EP1978069A1 - Thermally interlinking polyacrylate and method for its manufacture - Google Patents

Abstract

The crosslinker-accelerator system for the thermal cross-linking of polyacrylate with functional groups, comprises a bi-functional epoxide containing substance and an active substance accelerating at a temperature below the fusing temperature of the polyacrylates for the linkage reaction. The functional groups are suitable for linkage reactions with epoxy groups. An independent claim is included for a procedure for thermal cross-linking of polyacrylate.

Description

The invention relates to a process for the thermal crosslinking of polyacrylates, to a crosslinker-accelerator system for such crosslinking, and to correspondingly prepared thermally crosslinking or crosslinked polyacrylates.

For high-quality industrial applications, in particular also as adhesives, pressure-sensitive adhesives or heat sealants, among others polyacrylates are used, since these have been found to be well suited for the growing requirements in these application areas.
Adhesive compositions must have a good tack, but also meet high shear strength requirements. At the same time, good processability, in particular a high suitability for coating these compositions on support materials, must be ensured. This is achieved in particular by high molecular weight polyacrylates, high polarity and subsequent efficient crosslinking. In addition, polyacrylates can be produced in a transparent and weather-stable manner.

When coating polyacrylate compositions from solution or as a dispersion which can be used, for example, as pressure-sensitive adhesives, viscoelastic supports or heat sealants, thermal crosslinking has long been state of the art. As a rule, the thermal crosslinker-for example a multifunctional isocyanate, a metal chelate or a multifunctional epoxide-is used to dissolve a polyacrylate suitably equipped with functional groups, coated flat on a substrate with the aid of a doctor blade or stripper and then dried. As a result, diluents - ie organic solvents or water in the case of the dispersions - evaporated and the polyacrylate crosslinked accordingly. The crosslinking is very important for the coatings, because they get a sufficient cohesion and thermal resistance. Without crosslinking, the coatings would be too soft and would melt even at low load. Essential for a good coating result is the observance of the pot life (processing time in which the system is in the processable state), which can be significantly different depending on the crosslinking system. If this time is too short, then the crosslinker has already reacted in the polyacrylate solution, the solution is already cross-linked (angegelt or vergelt) and not evenly coatable.

Especially for reasons of environmental protection, the technological process for the production of PSAs is developing ever further. With more restrictive environmental regulations and rising solvent prices, efforts are being made to eliminate solvents from the polymer manufacturing process as much as possible. In industry, therefore, melt processes (also referred to as hot melt processes or hotmelt processes) with solvent-free coating technology are of increasing importance for the production of polymers, in particular of PSAs. In this case, meltable polymer compositions, ie those polymer compositions which, at elevated temperatures, pass into the flowable state without decomposing, are processed. Such compounds can be excellently processed from this melted state. In further developments of this process, the production can also be carried out solvent-poor or solvent-free.

The introduction of hotmelt technology places growing demands on adhesives. In particular, the aforementioned meltable polyacrylate compositions (other designations: "Polyacrylathotmelts", "Acrylathotmelts") are being examined very intensively for improvements. In the coating of polyacrylate compositions from the melt, thermal crosslinking has hitherto not been very widespread, although this process would have advantages.

• im Falle der Vernetzung mittels UV-Strahlen sind nur UV-transparente (UVdurchlässige) Schichten vernetzbar,
• im Falle der Vernetzung mit Elektronenstrahlen (Elektronenstrahlvernetzung bzw. Elektronenstrahlenhärtung, auch ESH) besitzen die Elektronenstrahlen nur eine begrenzte Eindringtiefe, die abhängig von Dichte des bestrahlten Materials und von der Beschleunigerspannung ist,
• in beiden vorgenannten Verfahren weisen die Schichten nach der Vernetzung ein Vernetzungsprofil auf, und die Haftklebeschicht vernetzt nicht homogen

Die Haftklebeschicht muss relativ dünn sein, damit man gut vernetzte Schichten erhält. In Abhängigkeit von Dichte, Bescheunigerspannung (ESH) und aktiver Wellenlänge (UV) variiert die durchstrahlbare Dicke zwar, ist aber immer stark limitiert, so dass sich nicht beliebig dicke Schichten durchvernetzen lassen, und zwar schon gar nicht homogen.So far, acrylate hotmelts are mainly crosslinked by radiation-chemical methods (UV irradiation, ESH radiation). However, this procedure is associated with various disadvantages:

• in the case of crosslinking by means of UV rays, only UV-transparent (UV-permeable) layers can be crosslinked,
• in the case of crosslinking with electron beams (electron beam crosslinking or electron beam curing, also ESH), the electron beams have only one limited penetration, which depends on the density of the material being irradiated and on the accelerator voltage,
• In both of the aforementioned methods, the layers have a crosslinking profile after crosslinking, and the pressure-sensitive adhesive layer does not crosslink homogeneously

The pressure-sensitive adhesive layer must be relatively thin so that well-crosslinked layers are obtained. Depending on density, Bescheunigerspannung (ESH) and active wavelength (UV) Although the durchstrahlbare thickness varies, but is always very limited, so that can not be cross-arbitrarily thick layers, and certainly not homogeneous.

Also known in the art are some methods for thermally crosslinking acrylate hotmelts. In this case, a crosslinker is added to the acrylate melt prior to coating, then it is shaped and wound into a roll.

Direct thermal crosslinking of acrylate hotmelt compositions containing NCO-reactive groups is described in US Pat EP 0 752 435 A1 described. The blocking agent-free isocyanates used, in particular sterically hindered and dimerized isocyanates, require very drastic crosslinking conditions, so that a sensible technical implementation presents problems. The in the EP 0 752 435 A1 described procedure leads in the conditions that prevail in the case of processing from the melt, a rapid, relatively extensive cross-linking, so that a processing of the mass, especially with regard to a coating of support materials, is difficult. In particular, no very homogeneous adhesive layers can be obtained, as are required for many technical applications of adhesive tapes.

Furthermore, the use of blocked isocyanates is state of the art. A disadvantage of this concept is the release of blocking groups or fragments which have a negative effect on the adhesive properties. An example is US 4,524,104 A , Here, acrylate hot melt adhesives are described which can be crosslinked with blocked polyisocyanates together with cycloamidines or salts thereof as a catalyst. In this system, on the one hand, the necessary catalyst, but especially the resulting HCN, phenol, caprolactam or the like, can greatly impair the product properties. In addition, drastic conditions for the release of the reactive groups are often required in this concept. A significant product use is not yet known and also appears unattractive.

The DE 10 2004 044 086 A1 describes a process for the thermal crosslinking of acrylate hotmelt, in which a solvent-free functionalized acrylate copolymer, which has a sufficiently long processing time for compounding, conveying and coating after addition of a thermally reactive crosslinker, preferably by means of a rolling process on a web-shaped layer of another material, in particular a belt-shaped carrier material or an adhesive layer, is coated and which post-coats after the coating under mild conditions until a sufficient for pressure-sensitive adhesive tapes cohesion is achieved.
A disadvantage of this process is that the free processing time and the degree of crosslinking are predetermined by the reactivity of the crosslinker (isocyanate). When using isocyanates, these react in part even when added, which depending on the system, the gel-free time can be very short. A mass with a higher proportion of functional groups such as hydroxyl groups or carboxylic acid is then no longer sufficiently coatable in the coatings. A streaky, interspersed with gel specks, so inhomogeneous line image would be the result.
Furthermore, there is the problem that the achievable degree of crosslinking is limited. If a higher degree of crosslinking is desired by adding a higher amount of crosslinker, this has disadvantages when using multifunctional isocyanates. The mass would react too fast and would be coatable - if at all - only with a very short processing time and thus a very high coating speed, which would increase the problem of the non-homogeneous coating image.

The DE 100 08 841 A1 describes polyacrylates accessible by thermal crosslinking of a polymer blend containing tert-butoxycarbonyl (BOC) protecting groups, a cationic photoinitiator and a bifunctional isocyanate and / or bifunctional epoxide. Also described is a process for the preparation of crosslinked polyacrylates in which the polymers to be crosslinked are first protected by introduction of tert-butoxycarbonyl groups and the crosslinking takes place only after deprotection by thermal treatment of the now deprotected polyacrylates. The introduction of the protective groups serves to avoid the crosslinking reaction which is only intended later, when high process temperatures are already present during early processing stages, as is the case, for example, in the hotmelt process. The protection applies in particular to the crosslinking reaction at this point in time, but also to all other competing reactions to the unprotected functional groups of the polymer to be processed, in particular on its hydroxide groups would attack.
A disadvantage of the process presented there, that the reactive groups must be released after the coating only by UV irradiation. As a result, the drawbacks already mentioned above for radiation-induced crosslinking (UV irradiation) apply to thermal crosslinking. In addition, flammable isobutene is released.

EP 1 317 499 A describes a process for crosslinking polyacrylates via UV-initiated epoxide crosslinking in which the polyacrylates have been functionalized with corresponding groups during the polymerization. The process offers shear strength advantages of the crosslinked polyacrylates over conventional crosslinking mechanisms, particularly over electron beam crosslinking. In this document, the use of di- or multifunctional oxygen-containing compounds, in particular of di- or multifunctional epoxides or alcohols, as a crosslinking reagent for functionalized polyacrylates, in particular functionalized acrylate hotmelt PSA, is described.
Since the crosslinking is initiated by UV rays, the disadvantages mentioned above also arise here.

As a result of the crosslinking with multifunctional epoxides, polyacrylate compositions, in particular polyacrylate hot-melt pressure-sensitive adhesives, have hitherto not been readily crosslinkable, and therefore this type of crosslinking can not be used industrially for a production process.

The object of the invention is to enable a thermal crosslinking of melt-processable polyacrylate compositions ("polyacrylate hotmelts"), wherein a sufficiently long processing time ("pot life") should be available for processing from the melt, in particular compared with the pot life in the known thermal crosslinking systems for polyacrylate hotmelts. It should be possible to dispense with the use of protective groups, which would have to be removed again if necessary by actinic radiation or other methods. Furthermore, the degree of crosslinking of the polyacrylate mass should be adjusted to a desired level without adversely affecting the advantages of the process control.
In the following, the polyacrylate compositions are also referred to in a synonymous manner as "polyacrylates". For the non-crosslinked Polyacrylatmassen is also the The term "polymers" used for the crosslinked or crosslinked polyacrylate masses the term "polymers".

Surprisingly, it has been found that a crosslinker-accelerator system ("crosslinking system") comprising at least one epoxide group-containing substance as crosslinker and at least one at a temperature below the melting temperature of a polyacrylate to be crosslinked for crosslinking reactions by means of epoxide-containing compounds accelerating substance acting as accelerator to one outstanding solution of the stated task.
An accelerating substance means that the substance supports the crosslinking reaction in so far as it provides for a sufficient reaction rate according to the invention, while the crosslinking reaction in the absence of the accelerator at selected reaction parameters, in particular a temperature below the melting temperature of the polyacrylates, not or only would be insufficiently slow. The accelerator thus ensures a significant improvement in the reaction kinetics of the crosslinking reaction. This can be done according to the invention in a catalytic manner, but also by integration into the reaction process.

The polyacrylates to be crosslinked contain functional groups which are suitable for entering into linking reactions with epoxide groups-in particular in the sense of addition reactions or substitution reactions.
Epoxides without appropriate accelerators react only under the influence of heat, in particular only after a prolonged supply of thermal energy. Although the known accelerator substances such as ZnCl ₂ lead to improve the reactivity in the temperature range of the melt, but in the absence of supply of thermal energy from the outside (ie, for example, at room temperature), the reactivity of the epoxides is lost even in the presence of accelerators, so that the crosslinking reaction stops (So they do not accelerate at the given temperature in the sense above). This is a particular problem when the polyacrylates processed as hotmelt are coated within relatively short periods of time (a few minutes) and then rapidly cool to room temperature or storage temperature for lack of further heat input. Without the initiation of a further crosslinking reaction, it would not be possible to achieve high degrees of crosslinking, which is especially true for many applications of polyacrylates, in particular the Use as a pressure-sensitive adhesive, would result in too low a cohesion of the mass.
If the crosslinker system were added to the polyacrylate system too early with only heat-functional accelerators, for example epoxy crosslinkers in the presence of ZnCl ₂ (in order to achieve a sufficient degree of crosslinking), then the masses could no longer be homogeneously processed, in particular compounded and compounded coat, because the masses too fast too high network or even gel ("unchecked" network) would.

A transfer to hotmelt systems was therefore not obvious to the person skilled in the art.
Only through the inventive combination of these components, a thermal crosslinking process could be offered that in the processing of the polyacrylate hot melt compositions, ie in the melt, does not lead to uncontrolled reactions (gel mass) and for processing a sufficiently long time (pot life) so that a uniform and bubble-free line image can be created especially when stripped as a layer or applied to a substrate. The crosslinker-accelerator system is also capable of further crosslinking the polyacrylate after processing, in particular after deletion as a layer or application to a support, with significantly reduced supply of thermal energy than to obtain the melt, ie after cooling without the need for actinic radiation would be necessary.

In particular, the polyacrylates by the crosslinker-accelerator system in a position without further active, so procedurally, supplied thermal energy (heating), especially after cooling to room temperature (RT, 20 ° C) or to a temperature near room temperature, on to network. In particular, heating can be dispensed with in this phase of the crosslinking without this leading to a termination of the crosslinking reaction.

The main claim therefore relates to a crosslinker-accelerator system for the thermal crosslinking of polyacrylates, comprising at least one epoxide-containing substance - as crosslinker - and at least one at a temperature below the melting temperature of the polyacrylate, in particular at room temperature, for the linking reaction accelerating substance ("Accelerator"); especially multifunctional amines. In this case, the crosslinker-accelerator system is used in particular in the presence of functional groups which can undergo a linking reaction with epoxide groups, in particular in the form of an addition or substitution. Thus, it is preferable to link the building blocks carrying the functional groups with the building blocks carrying the epoxide groups (in particular in the sense of crosslinking the corresponding polymer building blocks carrying the functional groups via the substances carrying epoxide groups as linking bridges).

Another aspect of the invention relates to a crosslinking process for polyacrylates, which can be carried out by means of the crosslinker-accelerator system according to the invention; in particular a process for the thermal crosslinking of melt-processible polyacrylate PSAs, in which the crosslinker-accelerator system described above is used.

If in the following in connection with the method according to the invention information on advantageous embodiments of the crosslinker accelerator system used are made, so for example advantageous compositions and the like, they should also for the inventive crosslinker accelerator system as such - even without direct reference to the procedural representations and claims - apply.

The epoxide group-containing substances are, in particular, multifunctional epoxides, ie those having at least two epoxide groups, corresponding to an overall indirect linking of the functional group-carrying components.

The process according to the invention offers in an outstanding, unexpected manner the advantage that a stable crosslinking process for polyacrylates can be offered, namely with excellent control over the crosslinking image through extensive decoupling of degree of crosslinking and reactivity (reaction kinetics).

The inventive method is used advantageously for the thermal crosslinking of polyacrylates. It is a polyacrylate (hereinafter simply as "Polyacrylate"), in particular a polyacrylate copolymer, based on acrylic acid esters and / or methacrylic acid esters, wherein at least a portion of the acrylic acid esters and / or methacrylic acid ester contains functional groups which react with epoxide groups in the manner described above, in particular to form a covalent bond can.

The crosslinked polyacrylates can be used for all possible applications in which a certain cohesion in the mass is desired. The process is particularly favorable for polyacrylate-based viscoelastic materials. A special field of application of the method according to the invention is the thermal crosslinking of PSAs, in particular hot melt PSAs.

In the method according to the invention, it is particularly advantageous to initiate the crosslinking in the melt of the polyacrylate and then to cool it at a time at which the polyacrylate is still outstandingly processable, ie, for example, homogeneously coatable and / or excellently formable. In particular, for adhesive tapes, a homogeneous, uniform line image is required, with no lumps, specks or the like to be found in the adhesive layer. Correspondingly homogeneous polyacrylates are also required for the other application forms.
The formability or coatability is given if the polyacrylate is not yet or only to a low degree crosslinked; Advantageously, the degree of crosslinking at the beginning of the cooling is not more than 10%, preferably not more than 3%, more preferably not more than 1%. The crosslinking reaction proceeds even after cooling until the finite degree of crosslinking is reached.
The term "cool down" here and in the following also includes passive cooling by removal of the heating.

The process according to the invention can be carried out in particular in such a way that crosslinking in the melt of the polyacrylate in the presence of the crosslinker, in particular the crosslinker-accelerator system, is initiated (ie thermally), preferably at a time shortly before further processing, in particular molding or coating. This usually takes place in a processing reactor (compounder, for example an extruder). The mass is then removed from the compounder and further processed and / or shaped as desired. In the Processing or molding or thereafter, the polyacrylate is cooled by actively cooling and / or heating is stopped or by the polyacrylate is heated to a temperature below the processing temperature (possibly also here after previous active cooling) when the temperature is not up should fall to room temperature.

The further processing or shaping can be advantageous in particular the coating on a permanent or temporary carrier.

In a very advantageous variant of the invention, the polyacrylate is coated on a permanent or temporary carrier during or after removal from the processing reactor and during the coating or after the coating, the polyacrylate mass is cooled to room temperature (or a temperature close to room temperature), especially immediately after the coating.

Initiation "shortly before" the further processing means, in particular, that at least one of the components required for crosslinking (in particular the substances containing epoxide groups and / or the accelerator) is added as late as possible in the hotmelt (ie in the melt) (homogeneous processability due to even small amounts) Degree of crosslinking, see above), but as early as necessary, that a good homogenization with the polymer composition takes place.

The crosslinker-accelerator system is chosen so that the crosslinking reaction proceeds at a temperature below the melting temperature of the polyacrylate composition, especially at room temperature. The possibility of networking at room temperature offers the advantage that no additional energy must be supplied and therefore a cost savings can be booked.
The term "crosslinking at room temperature" refers in particular to the crosslinking at conventional storage temperatures of adhesive tapes, viscoelastic non-sticky materials or the like and should not be limited to 20 ° C in so far. Of course, it is also advantageous according to the invention if the storage temperature deviates from 20 ° C due to weather-related or other temperature fluctuations - or the room temperature differs due to local conditions of 20 ° C - and the networking - in particular without further energy supply - progresses.

In particular, multifunctional epoxides are used as substances containing epoxide groups, ie those which have at least two epoxide units per molecule (ie are at least bifunctional). These may be both aromatic and aliphatic compounds.

Excellent multifunctional epoxides are oligomers of epichlorohydrin, polyether polyhydric alcohols [especially ethylene, propylene and butylene glycols, polyglycols, thiodiglycols, glycerine, pentaerythritol, sorbitol, polyvinyl alcohol, polyallylalcohol and the like], epoxy ethers of polyhydric phenols [especially resorcinol, hydroquinone, bis - (4-hydroxyphenyl) -methane, bis (4-hydroxy-3-methylphenyl) -methane, bis (4-hydroxy-3,5-dibromophenyl) -methane, bis- (4-hydroxy-3,5- difluorophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) -propane, 2 , 2-bis- (4-hydroxy-3-chlorophenyl) -propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) -propane, 2,2-bis- (4-hydroxy-3, 5-dichlorophenyl) -propane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -4'-methylphenylmethane, 1, 1-bis (4-hydroxyphenyl) -2,2,2-trichloroethane, bis (4-hydroxyphenyl) - (4-chlorophenyl) -methane, 1,1-B is- (4-hydroxyphenyl) -cyclohexane, bis (4-hydroxyphenyl) -cyclohexylmethane, 4,4'-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 4,4'-dihydroxydiphenylsulfone] and their hydroxyethyl ether, phenol-formaldehyde condensation products such as phenol alcohols, phenol-aldehyde resins and similar, S- and N-containing epoxides (for example N, N-diglycidylanillin, N, N'-dimethyldiglycidyl-4,4-diaminodiphenylmethane) and also epoxides which are prepared by conventional methods from polyunsaturated carboxylic acids or mono- or polyunsaturated carboxylic acids unsaturated carboxylic acid residues of unsaturated alcohols, glycidyl esters, polyglycidyl esters which can be obtained by polymerization or copolymerization of glycidyl esters of unsaturated acids or from other acidic compounds (cyanuric acid, diglycidyl sulfide, cyclic trimethylene trisulfone or derivatives thereof and others) are obtainable.
Very suitable ethers are, for example, 1,4-butanediol diglycidyl ether, polyglycerol-3-glycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, neopentyl glycol diglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.

As accelerators, particular preference is given to amines (formally as substitution products of ammonia, in the following formulas these substituents are represented by "R" and include in particular alkyl and / or aryl radicals and / or other organic radicals), particularly preferably those amines which react with the building blocks of the polyacrylates little or no reactions.

In principle, it is possible to select both primary (NRH ₂ ), secondary (NR ₂ H) and tertiary amines (NR ₃ ) as accelerators, of course also those which have a plurality of primary and / or secondary and / or tertiary amine groups. However, especially preferred accelerators are tertiary amines, in particular in connection with the abovementioned reasons, such as, for example, triethylamine, triethylenediamine, benzyldimethylamine, dimethylamino-methylphenol, 2,4,6-tris- (N, N-dimethylaminomethyl) -phenol, N, N 'urea-bis (3- (dimethyl-amino) propyl).

Advantageously, multifunctional amines such as diamines, triamines and / or tetramines can also be used as accelerators.
For example, diethylenetriamine, triethylenetetramine, trimethylhexamethylenediamine,

Further excellent accelerators are pyridine, imidazoles (such as 2-methylimidazole), 1,8-diazabicyclo (5.4.0) undec-7-ene. Cycloaliphatic polyamines can also be used excellently as accelerators.

Also suitable are phosphate-based accelerators, such as phosphines and / or phosphonium compounds, for example triphenylphosphine or tetraphenylphosphonium tetraphenylborate.

The composition to be crosslinked according to the invention comprises at least one polyacrylate. This is a polymer which is obtainable by radical polymerization of acrylic monomers, which are also understood to mean methylacrylic monomers, and optionally other copolymerizable monomers.

It is preferably a polyacrylate crosslinkable with epoxide groups. Accordingly, as monomers or comonomers it is preferred to use functional monomers crosslinkable with epoxide groups; in particular monomers having acid groups (especially carboxylic acid, sulfonic acid or phosphonic acid groups) and / or hydroxyl groups and / or acid anhydride groups and / or epoxide groups and / or amine groups are used; preferred are carboxylic acid group-containing monomers. It is particularly advantageous if the polyacrylate has copolymerized acrylic acid and / or methacrylic acid.
Other monomers which can be used as comonomers for the polyacrylate are, for example, acrylic acid and / or methacrylic acid esters having up to 30 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenic unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and 1 or 2 double bonds or mixtures of these monomers.

For the process according to the invention, preference is given to using a polyacrylate which comprises, in addition to the following educt mixture containing in particular softening monomers, monomers having functional groups capable of reacting with the epoxy groups, in particular addition and / or substitution reactions, and optionally other einpolymerisierbnare comonomers, in particular hardening monomers. The nature of the polyacrylate to be prepared (pressure-sensitive adhesive, heat sealant, viscoelastic non-sticky material and the like) can be influenced in particular by varying the glass transition temperature of the polymer by different weight proportions of the individual monomers.
For purely crystalline systems, there is a thermal equilibrium between crystal and liquid at the melting point T _s . By contrast, amorphous or partially crystalline systems are characterized by the transformation of the more or less hard amorphous or partially crystalline phase into a softer (rubbery to viscous) phase. At the glass transition, in particular in polymeric systems, "thawing" (or "freezing" upon cooling) of the Brownian motion of longer chain segments occurs.
The transition from the melting point T _S (also called "melting temperature", actually defined only for purely crystalline systems; "polymer crystals") to the glass transition point T _G (also "Glass transition temperature", "glass transition temperature") can therefore be considered as flowing, depending on the proportion of the partial crystallinity of the sample investigated.
In the context of this document, in the sense of the above embodiments, the melting point is also included in the specification of the glass point, ie the melting point for the corresponding "melting" systems is understood as the glass transition point (or equivalently also as the glass transition temperature). The data of the glass transition temperatures refer to the determination by means of dynamic mechanical analysis (DMA) at low frequencies.
To obtain polymers, for example pressure-sensitive adhesives or heat sealants, with desired glass transition temperatures, the quantitative composition of the monomer mixture is advantageously chosen such that according to an equation (G1) in analogy to the Fox equation (cf. TG Fox, Bull. Phys. Soc. 1 (1956) 123 ) gives the desired T _G value for the polymer. $$\frac{\mathrm{1}}{{\mathrm{T}}_{\mathrm{G}}}\mathrm{=}{\displaystyle \underset{\mathrm{n}}{\mathrm{\Sigma }}}\frac{{\mathrm{W}}_{\mathrm{n}}}{{\mathrm{T}}_{\mathrm{G}\mathrm{.}\mathrm{n}}}$$

Here n represents the number of runs via the monomers used, w _n the mass fraction of the respective monomer n (wt .-%) and T _{G, n} the respective glass transition temperature of the homopolymer of the respective monomers n in K.

1. a) Acrylsäureester und/oder Methacrylsäureester der folgenden Formel
   
            CH₂ = C(R^I)(COOR^II)
   
   wobei R^I = H oder CH₃ und R^II ein Alkylrest mit 4 bis 14 C-Atomen ist,
2. b) olefinisch ungesättigte Monomere mit funktionellen Gruppen der für eine Reaktivität mit Epoxidgruppen bereits definierten Art,
3. c) optional weitere Acrylate und/oder Methacrylate und/oder olefinisch ungesättigte Monomere, die mit der Komponente (a) copolymerisierbar sind.

Preference is given to using a polyacrylate which can be attributed to the following monomer composition:

1. a) acrylic acid esters and / or methacrylic acid esters of the following formula
   
   CH ₂ = C (R ^I ) (COOR ^II )
   
   where R ^I = H or CH ₃ and R ^{II is} an alkyl radical having 4 to 14 C atoms,
2. b) olefinically unsaturated monomers having functional groups already defined for reactivity with epoxide groups,
3. c) optionally further acrylates and / or methacrylates and / or olefinically unsaturated monomers which are copolymerizable with component (a).

To use the polyacrylate as a pressure-sensitive adhesive, the proportions of the corresponding components (a), (b), and (c) are selected such that the polymerization product in particular has a glass transition temperature ≦ 15 ° C. (DMA at low frequencies).

It is very advantageous for the preparation of pressure-sensitive adhesives, the monomers of component (a) in a proportion of 45 to 99 wt .-%, the monomers of component (b) in an amount of 1 to 15 wt .-% and the monomers of Component (c) in a proportion of 0 to 40 wt .-% to choose (the statements are based on the monomer mixture for the "base polymer", ie without additions of any additives to the finished polymer, such as resins etc).

For the application of a hot melt adhesive, that is to say a material which becomes tacky only by heating, the proportions of the corresponding components (a), (b), and (c) are chosen in particular such that the copolymer has a glass transition temperature (T _G ) between 15 ° C and 100 ° C, preferably between 30 ° C and 80 ° C, more preferably between 40 ° C and 60 ° C. The proportions of components (a), (b), and (c) should be selected accordingly.

A viscoelastic material, which for example can typically be laminated on both sides with pressure-sensitively adhesive layers, has in particular a glass transition temperature (T _G ) of between -50 ° C. and + 100 ° C., preferably between -20 ° C. and + 60 ° C., particularly preferably 0 ° C up to 40 ° C. The proportions of components (a), (b), and (c) should also be chosen accordingly.

The monomers of component (a) are, in particular, plasticizing and / or nonpolar monomers.
For the monomers (a), preference is given to using acrylic monomers which comprise acrylic and methacrylic acid esters having alkyl groups consisting of 4 to 14 C atoms, preferably 4 to 9 C atoms. Examples of such monomers are n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-amyl acrylate, n-hexyl acrylate, hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, isobutyl acrylate, isooctyl acrylate , Isooctylmethacrylat, and their branched isomers, such as. For example, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate.

The monomers of component (b) are, in particular, olefinic unsaturated monomers (b) having functional groups, in particular having functional groups capable of undergoing reaction with the epoxide groups.

For component (b) it is preferred to use monomers having such functional groups selected from the following list: hydroxy, carboxy, sulfonic acid or phosphonic acid groups, acid anhydrides, epoxides, amines.
Particularly preferred examples of monomers of component (b) are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, β-acryloyloxypropionic acid, trichloroacrylic acid, vinylacetic acid, vinylphosphonic acid, itaconic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 6 Hydroxyhexyl methacrylate, allyl alcohol, glycidyl acrylate, glycidyl methacrylate.

In principle, in the sense of component (c), all vinylic-functionalized compounds which are copolymerisable with component (a) and / or component (b) can be used, and can also serve for adjusting the properties of the resulting PSA.

Exemplary monomers for component (c) are:
Methylacrylate, ethylacrylate, propylacrylate, methylmethacrylate, ethylmethacrylate, benzylacrylate, benzylmethacrylate, sec-butylacrylate, tert-butylacrylate, phenylacrylate, phenylmethacrylate, isobornylacrylate, isobornylmethacrylate, t-butylphenylacrylate, t-butylaphenylmethacrylate, dodecylmethacrylate, isodecylacrylate, laurylacrylate, n-undecylacrylate, stearylacrylate , Tridecyl acrylate, behenyl acrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-butoxy-ethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,5-dimethyladamantyl acrylate, 4-cumylphenyl methacrylate, cyanoethyl acrylate, cyanoethyl methacrylate, 4-biphenyl acrylate , 4-biphenyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, tetrahydrofufuryl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, 2-butoxyethyl acrylate, 2-butoxyethyl methacrylate, 3-methoxyacrylic acid methyl ester, 3-methoxybutyl acrylate, Phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-phenoxyethyl methacrylate, butyl diglycol methacrylate, ethylene glycol acrylate, ethylene glycol monomethyl acrylate, methoxy polyethylene glycol methacrylate 350, methoxy polyethylene glycol methacrylate 500, propylene glycol monomethacrylate, butoxy diethylene glycol methacrylate, ethoxy triethylene glycol methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 1,1,1,3,3, 3-Hexafluoroisopropylacrylat, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2,2,3,3,4, 4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8, 8-Pentadecafluorooctylmethacrylat,
Dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, N- (1-methylundecyl) acrylamide, N- (n-butoxymethyl) acrylamide, N- (butoxymethyl) methacrylamide, N- (ethoxymethyl) acrylamide, N- (n-octadecyl) acrylamide, furthermore N, N- Dialkyl-substituted amides, such as N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-benzylacrylamides, N-isopropylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide,
Acrylonitrile, methacrylonitrile, vinyl ethers such as vinyl methyl ether, ethyl vinyl ether, vinyl isobutyl ether, vinyl esters such as vinyl acetate, vinyl chloride, vinyl halides, vinylidene chloride, vinylidene halides, vinylpyridine, 4-vinylpyridine, N-vinylphthalimide, N-vinyllactam, N-vinylpyrrolidone, styrene, a- and p Methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, 3,4-dimethoxystyrene. Macromonomers such as 2-polystyrene ethyl methacrylate (molecular weight Mw from 4000 to 13000 g / mol), poly (methyl methacrylate) ethyl methacrylate (Mw from 2000 to 8000 g / mol).

Monomers of component (c) may advantageously also be chosen such that they contain functional groups which promote a subsequent radiation-chemical crosslinking (for example by electron beams, UV). Suitable copolymerizable photoinitiators are e.g. Benzoin acrylate and acrylate-functionalized benzophenone derivatives. Monomers that promote electron beam crosslinking, e.g. Tetrahydrofufuryl acrylate, N-tert-butylacrylamide, allyl acrylate, this list is not exhaustive.

Preparation of the polymers

The preparation of the polyacrylates can be carried out by the methods familiar to the person skilled in the art, in particular advantageously by conventional free-radical polymerizations or controlled free-radical polymerizations. The polyacrylates can be prepared by copolymerization of the monomeric components using the usual polymerization initiators and optionally regulators, wherein polymerized at the usual temperatures in bulk, in emulsion, for example in water or liquid hydrocarbons, or in solution.
The polyacrylates are preferably prepared by polymerization of the monomers in solvents, in particular in solvents having a boiling range of from 50 to 150 ° C., preferably from 60 to 120 ° C., using the usual amounts of polymerization initiators, generally from 0.01 to 5, in particular 0.1 to 2 wt .-% (based on the total weight of the monomers) is prepared.
In principle, all conventional acrylates familiar to the person skilled in the art are suitable. Examples of radical sources are peroxides, hydroperoxides and azo compounds, for example dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-t-butyl peroxide, cyclohexyl sulfonyl acetyl peroxide, diisopropyl percarbonate, t-butyl peroctoate, benzpinacol. In a very preferred procedure, the radical initiator used is 2,2'-azobis (2-methylbutyronitrile) (Vazo® 67 ™ from DuPont) or 2,2'-azobis (2-methylpropionitrile) (2,2'-azobisisobutyronitrile;AIBN; Vazo® 64 ™ from DuPont).
The solvents used are alcohols, such as methanol, ethanol, n- and iso-propanol, n- and iso-butanol, preferably isopropanol and / or isobutanol; and hydrocarbons such as toluene and in particular gasoline having a boiling range of 60 to 120 ° C in question. In particular, ketones, such as preferably acetone, methyl ethyl ketone, methyl isobutyl ketone and esters, such as ethyl acetate and mixtures of solvents of the type mentioned can be used, mixtures containing isopropanol, in particular in amounts of 2 to 15 wt .-%, preferably 3 to 10 wt. %, based on the solution mixture used, are preferred.
The weight-average molecular weights M _{w of} the polyacrylates are preferably in a range from 20,000 to 2,000,000 g / mol; very preferably in a range of 100,000 to 1,000,000 g / mol, most preferably in a range of 150,000 to 500,000 g / mol [the data of the average molecular weight M _w and the polydispersity PD in this document refer to the determination by gel permeation chromatography ( see measuring method A3, experimental part)]. For this purpose, it may be advantageous to carry out the polymerization in the presence of suitable polymerization regulators such as thiols, halogen compounds and / or alcohols in order to set the desired average molecular weight.

The polyacrylate preferably has a K value of from 30 to 90, more preferably from 40 to 70, measured in toluene (1% solution, 21 ° C). The K value according to Fikentscher is a measure of the molecular weight and viscosity of the polymer.

Particularly suitable for the process according to the invention are polyacrylates which have a narrow molecular weight distribution (polydispersity PD <4). Despite relatively low molecular weight after crosslinking, these compositions have a particularly good shear strength. In addition, the lower molecular weight allows for easier melt processing because the flow viscosity is less than that of a more widely dispersed polyacrylate with largely similar application properties. Narrowly distributed polyacrylates can be advantageously prepared by anionic polymerization or by controlled radical polymerization, the latter being particularly well suited. Examples of such polyacrylates which are prepared by the RAFT process are described in US Pat US 6,765,078 B2 and US 6,720,399 B2 described. Also via N-Oxyle can be prepared corresponding polyacrylates, such as in the EP 1 311 555 B1 is described. Atom Transfer Radical Polymerization (ATRP) can also be used advantageously for the synthesis of narrowly distributed polyacrylates, preference being given to monofunctional or difunctional secondary or tertiary halides as initiator and to abstraction of the halide (s) Cu, Ni, Fe , Pd, Pt, Ru, Os, Rh, Co, Ir, Ag or Au complexes (cf., for example EP 0 824 111 A1 ; EP 826 698 A1 ; EP 824 110 A1 ; EP 841 346 A1 ; EP 850 957 A1 ) are used. The different possibilities of ATRP are also in the scriptures US 5,945,491 A . US 5,854,364 A and US 5,789,487 A described.

At least one tackifying resin may be added to the polyacrylates obtainable by the process according to the invention prior to thermal crosslinking. Suitable tackifying resins to be added are the previously known adhesive resins described in the literature. In particular, reference is made to all aliphatic, aromatic, alkylaromatic hydrocarbon resins, hydrocarbon resins based on pure monomers, hydrogenated hydrocarbon resins, functional hydrocarbon resins and natural resins. It is preferable to use pinene, indene and rosin resins, their disproportionated, hydrogenated, polymerized, esterified derivatives and salts, terpene resins and terpene-phenolic resins, and also C5, C9 and other hydrocarbon resins. Also, combinations of these and other resins can be used advantageously to adjust the properties of the resulting adhesive as desired. It is particularly preferable to use all the (poly) compatible (soluble) resins. In a special preferred procedure are terpenphenol resins and / or rosin esters added.

Optionally, also powdered and granular fillers, dyes and pigments, especially abrasive and reinforcing, such as chalks (CaCO ₃ ), titanium dioxides, zinc oxides and carbon blacks also to high levels, that is from 1 to 50 wt .-%, based on the total formulation, excellently dosed into the polyacrylate melt, homogeneously incorporated and coated on the 2-roll applicator. Here often the conventional methods fail because of the then very high viscosity of the total compound.

Very preferably, different types of chalk can be used as filler, with microsoluble chalk being particularly preferably used. With preferred proportions of up to 30% by weight, the technical adhesive properties (shear strength at RT, instantaneous bond strength to steel and PE) practically do not change as a result of the filler addition.

Furthermore, flame retardant fillers such as ammonium polyphosphate may further include electrically conductive fillers (such as carbon black, carbon fibers and / or silver coated spheres), thermally conductive materials (such as boron nitride, alumina, silicon carbide), and ferromagnetic additives (such as ferric (III ) -oxides), further additives for increasing the volume, in particular for producing foamed layers (such as blowing agents, glass beads, hollow glass spheres, microspheres of other materials, expandable microballoons, silica, silicates, organically renewable raw materials, such as wood flour, organic and / or inorganic nanoparticles , Fibers), furthermore anti-aging agents, light stabilizers, antiozonants, compounding agents and / or blowing agents are added or compounded before or after the concentration of the polyacrylate. As an anti-aging agent, preferably both primary, eg 4-methoxyphenol, and secondary anti-aging agents, eg Irgafos® TNPP from Ciba Geigy, can also be used in combination with one another. Reference should be made here to other corresponding Irganox® types from Ciba Geigy or Hostano® from Clariant. Phenothiazine (C-radical scavengers) and hydroquinone methyl ether in the presence of oxygen and oxygen itself can be used as further excellent anti-aging agents.

Optionally, the usual plasticizers (plasticizers), in particular in concentrations of up to 5 wt .-%, be added sets. As plasticizers, for example, low molecular weight polyacrylates, phthalates, water-soluble plasticizers, soft resins, phosphates, polyphosphates and / or citrates can be added.

Furthermore, optionally, the thermally crosslinkable Acrylathotmelt can also be blended or blended with other polymers. Suitable for this purpose are polymers based on natural rubber, synthetic rubber, EVA, silicone rubber, acrylic rubber, polyvinyl ethers. It proves to be expedient to add these polymers in granulated or otherwise comminuted form the Acrylathotmelt prior to addition of the thermal crosslinker. The preparation of the polymer blends takes place in an extruder, preferably in a multi-screw extruder or in a planetary roller mixer. To stabilize the thermally crosslinked acrylate hotmelts, in particular also polymer blends of thermally crosslinked acrylate hotmelts and other polymers, it may be useful to irradiate the molded material with electron irradiation of low doses. Optionally, crosslinking promoters such as di-, tri- or multifunctional acrylate, polyester and / or urethane acrylate can be added to the polyacrylate for this purpose.

Further process implementation

The concentration of the polymer can be done in the absence of the crosslinker and accelerator substances. However, it is also possible to add one of these classes of compounds to the polymer even before the concentration, so that the concentration then takes place in the presence of this substance (s).

The polymers are then transferred to a compounder. In particular embodiments of the process according to the invention, the concentration and the compounding can take place in the same reactor.
In particular, an extruder can be used as the compounder. The polymers are present in the compounder in the melt, either by being introduced already in the melt state or by being heated to melt in the compounder. In the compounder, the polymers are kept in the melt by heating.

As long as neither crosslinking agents (epoxides) nor accelerators are present in the polymer, the possible temperature in the melt is limited by the decomposition temperature of the polymer. The process temperature in the compounder is usually between 80 and 150.degree. C., in particular between 100 and 120.degree.

The epoxide group-containing substances are added to the polymer before or with the accelerator addition.
The epoxide group-containing substances can be added to the monomers already before or during the polymerization phase if they are sufficiently stable for them. Advantageously, however, the substances containing the epoxide groups are added to the polymer either before being added to the compounder or when added to the compounder, ie added to the compounder together with the polymers.

In a very advantageous procedure, the accelerator substances are added to the polymers shortly before the further processing of the polymers, in particular a coating or other shaping. The time window of the addition before the coating depends in particular on the available pot life, ie the processing time in the melt, without the properties of the resulting product being adversely affected. With the method according to the invention, pot lives of a few minutes to a few tens of minutes could be achieved (depending on the choice of experimental parameters), so that the accelerator should be added within this period before the coating. Advantageously, the accelerator is added as late as possible in the hotmelt, but as early as necessary, that there is still a good homogenization with the polymer composition.
Time spans of 2 to 10 minutes, in particular of more than 5 minutes, at a process temperature of 110 to 120 ° C. have proven to be very advantageous.

The crosslinkers (epoxides) and the accelerators can also both be added shortly before the further processing of the polymer, that is advantageous in the phase, as shown above for the accelerators. For this purpose, it is advantageous to simultaneously introduce the crosslinker-accelerator system into the process at one and the same point, also as an epoxide-accelerator mixture.

In principle, it is also possible to exchange the addition times or addition points of crosslinker and accelerator in the above-described embodiments, so that the accelerator can be added before the substances containing epoxide groups.

In the compounding process, the temperature of the polymer during the addition of the crosslinker and / or the accelerator is between 50 and 150.degree. C., preferably between 70 and 130.degree. C., particularly preferably between 80 and 120.degree.

It has basically proven to be very advantageous to add the crosslinker, ie the substance containing epoxide groups, to 0.1-5% by weight, based on the polymer without additives.

It is advantageous to add the accelerator to 0.05-5% by weight, based on the additive-free polymer.

It is particularly advantageous if the proportion of crosslinker is chosen such that an elastic fraction of the crosslinked polyacrylates is at least 20%. Preferably, the elastic fraction is at least 40%, more preferably at least 60% (in each case measured according to measurement method H3, see Experimental Part).

In principle, the number of functional groups, that is to say in particular the carboxylic acid groups, can be chosen such that it is present in excess with respect to the epoxide groups, ie that there are only sufficiently many functional groups in the polymer, ie potential crosslinking or linking sites in the polymer to achieve desired networking.
For the effect of the crosslinker-accelerator system according to the invention, in particular with regard to the process according to the invention including its variants, it is particularly advantageous to control the amounts of accelerator and crosslinker (substances containing epoxide groups) and optionally also the amount of crosslinking reaction reactive, To match functional groups in the polyacrylate and to optimize for the desired crosslinking result (see also the comments on the relevant relationships and the ability to control the process).

To indicate the ratios of the constituents of the crosslinker-accelerator system to one another, the ratio of the number of epoxide groups in the crosslinker to the number of reactive functional groups in the polymer can be used in particular. In principle, this ratio can be chosen freely, so that there is either an excess of functional groups, numerical equality of the groups or an excess of epoxide groups.
Advantageously, this ratio is chosen such that the epoxide groups are present in the deficit (to the maximum equality); Most preferably, the ratio of the total number of epoxide groups in the crosslinker to the number of functional groups in the polymer is in the range of 0.1: 1 to 1: 1.

Another key figure is the ratio of the number of acceleration-effective groups in the accelerator to the number of epoxide groups in the crosslinker. As acceleration-effective groups in particular secondary amine groups and tertiary amine groups are calculated. In principle, this ratio can also be chosen freely, so that there is either an excess of acceleration-effective groups, numerical equality of the groups or an excess of epoxide groups.
It is particularly advantageous if the ratio of the number of acceleration-effective groups in the accelerator to the number of epoxide groups in the crosslinker is from 0.2: 1 to 4: 1.

After compounding of the mass, the further processing of the polymer, in particular the coating, takes place on a permanent or on a temporary carrier (the permanent carrier remains in the application with the adhesive layer, while the temporary carrier in the further processing process, for example, the assembly of the adhesive tape , or in the application of the adhesive layer is removed again).

The coating of the self-adhesive compositions can be carried out using hotmelt coating nozzles known to the person skilled in the art or preferably using roller applicators, also known as coating calenders. The coating calenders can advantageously consist of two, three, four or more rolls.
Preferably, at least one of the rolls is provided with an anti-adhesive roll surface, preferably all rolls which come into contact with the polyacrylate. It can be equipped anti-adhesive all rollers of the calender in a favorable approach.

As an anti-adhesive roll surface, a steel-ceramic-silicone composite material is particularly preferably used. Such roll surfaces are resistant to thermal and mechanical stress.
Surprisingly, it has been found to be particularly advantageous for a person skilled in the art to use roll surfaces which have a surface structure, in particular such that the surface does not make complete contact with the polymer layer to be processed, but rather that the contact surface, compared with a smooth roll, is lower. Structured rolls, such as metal anilox rolls (for example steel grid rolls), are particularly favorable.

The coating can be particularly advantageous according to the coating method as described in the WO 2006/027387 A1 from page 12, line 5 to page 20, line 13, in particular under the sections "variant A" (page 12), "variant B" (page 13), "variant C" (page 15), "method D "(Page 17)," variant E "(page 19) and the figures Fig. 1 to 6 , The above-mentioned disclosure points from the WO 2006/027387 A1 are therefore explicitly included in the disclosure of the present document.

Particularly good results are obtained in the two-roll and three-roll calendering plants (compare in particular variants B). Fig. 3 , Variant C - Fig. 4 and variant D - Fig. 4 of the WO 2006/027387 A1 ) achieved by the use of calender rolls, which are equipped with anti-adhesive surfaces or with surface-modified rolls, here are particularly advantageous to mention metal anilox rolls. These metal anilox rollers, preferably steel anilox rollers, have a regularly geometrically discontinuous surface structure. This is particularly advantageous for the transfer roller ÜW. These surfaces contribute in a particularly advantageous manner to a success of the coating process, since anti-adhesive and structured surfaces allow the transfer of the polyacrylate composition even on anti-adhesive coated carrier surfaces. Various types of anti-adhesive surface coatings can be used for the calender rolls. Also particularly suitable here are, for example, the aforementioned metal-ceramic-silicone composites PALLAS SK-B-012/5 from PALLAS OBERFLÄCHENTECHNIK GMBH, Germany and AST 9984-B from ADVANCED SURFACE TECHNOLOGIES, Germany, proved.

In particular, the transfer rollers (ÜW) can be designed as steel anilox rollers (see variants B -. Fig. 3 , Variant C - Fig. 4 and variant D - Fig. 4 of the WO 2006/027387 A1 ). Particularly preferably used as a transfer roller ÜW be, for example, steel anilox rollers with the designation 140 L / cm and a web width of 10 .mu.m, for example those from the company Saueressig, Germany.

In the case of coating, coating speeds of up to 300 m / min can be achieved, in particular when using the multiroll calender.

At Fig. 1 The present document is exemplary, without wishing to be limited thereby, the compounding and coating process illustrated by a continuous flow. The polymers are added at the first entry point (1.1) into the compounder (1.3), here for example an extruder. Either the input is already in the melt, or the polymers are heated in the compounder to the melt. Advantageously, the epoxide-containing compounds are added to the compounder at the first input location with the polymer.
Shortly before the coating, the accelerators are added at a second input location (1.2). This has the result that the accelerators are added to the epoxide-containing polymers only shortly before the coating and the reaction time in the melt is low.

The reaction can also be carried out batchwise. In corresponding compounders such as reactor vessels, the addition of the polymers, the crosslinkers and the accelerators may be delayed in time and not, as in US Pat FIG. 1 represented, staggered place.

Immediately after the coating, preferably by means of roller application or by means of an extrusion nozzle, the polymer is only slightly cross-linked but not yet sufficiently cross-linked. The crosslinking reaction proceeds advantageously on the support.

After coating, the polymer composition cools relatively quickly, down to storage temperature, usually room temperature. The crosslinker-accelerator system according to the invention is suitable for allowing the crosslinking reaction to proceed without the supply of further thermal energy (without heat supply).

The crosslinking reaction between the functional groups of the polyacrylate and the epoxides by means of the crosslinker-accelerator system according to the invention runs completely even without heat supply under normal conditions (room temperature). As a rule, after a storage time of 5 to 14 days, the crosslinking has been completed so far that a functional product (in particular an adhesive tape or a functional carrier layer based on the polyacrylate) is present. The final state and thus the final cohesion of the polymer is expected to be earlier, depending on the choice of the polymer and the crosslinker-Beschleuiniger system after storage for 14 to 100 days, advantageously after 14 to 50 days storage at room temperature ,

The crosslinking increases the cohesion of the polymer and thus also the shear strength. The links are very stable. This allows very aging-resistant and heat-resistant products such as adhesive tapes, viscoelastic carrier materials or moldings.

The physical properties of the end product, in particular its viscosity, adhesive power and tack, can be influenced by the degree of crosslinking, so that the end product can be optimized by suitable choice of the reaction conditions. Various factors determine the process window of this process. The most important influencing variables are the amounts (concentrations and ratios to one another) and the chemical properties of the crosslinkers and the accelerators, the process and coating temperature, the residence time in compounders (in particular extruders) and in the coating unit, fraction of functional groups (in particular acid groups and / or Hydroxy groups) in the polymer and the average molecular weight of the polyacrylate.

In the following, some relationships in the production of the crosslinked self-adhesive composition according to the invention are described, which characterize the process of preparation in more detail, but are not meant to be limiting for the inventive concept.

The inventive method offers in an outstanding, unexpected way the advantage that a stable crosslinking process for polyacrylates can be offered, with an excellent control over the Cross-linking picture through extensive decoupling of degree of crosslinking and reactivity (reaction kinetics). The amount of crosslinker added (amount of epoxide) largely influences the degree of crosslinking of the product, the accelerator largely controls the reactivity.

Surprisingly, it was found that the degree of crosslinking could be selected by the amount of epoxide-containing substances added, largely independently of the otherwise selected process parameters of temperature and amount of added accelerator.

The influence of the epoxide group concentration on the degree of cross-linking with the same amount of accelerator and temperature is shown schematically Fig. 2 , The accelerator concentration increases from the concentration A (upper curve, low concentration) over the concentrations B (second lowest concentration) and C (second highest concentration) to the concentration D (lower curve, highest concentration). As it turns out, the final value of the degree of crosslinking - represented here by decreasing values of the micro-shear value - increases with increasing epoxide concentration, while the reaction kinetics remains virtually unaffected.

Furthermore, it was found that the added amount of accelerator had a direct influence on the crosslinking rate, thus also the time of reaching the final degree of crosslinking, without however absolutely influencing it. The reactivity of the crosslinking reaction can be selected so that the crosslinking leads to the desired degree of crosslinking within a few weeks even when the finished product is stored at the conditions customary there (room temperature), in particular without the thermal energy (active) still having to be supplied or that the product would have to be treated further.
The dependence of the curing time at constant temperature (here room temperature) and constant amount of epoxy is schematically in Fig. 3 played. The accelerator concentration increases from concentration 1 (upper curve, low concentration), above concentrations 2 (second lowest concentration) and 3 (second highest concentration) to concentration 4 (lower curve, highest concentration). Here it can be seen that the final value of the degree of crosslinking remains almost constant (with the lowest reaction this value has not yet been reached); this Value is achieved at high accelerator concentrations but faster than at low accelerator concentrations.

In addition to the aforementioned parameters, the reactivity of the crosslinking reaction can also be influenced by varying the temperature, if desired, especially in those cases where the advantage of "intrinsic crosslinking" during storage under normal conditions is irrelevant. At constant crosslinker concentration, increasing the process temperature leads to a reduced viscosity, which improves the coatability of the composition, but reduces the processing time.

An increase in processing time is obtained by reducing the accelerator concentration, lowering the molecular weight, reducing the concentration of functional groups in the polymer, reducing the acid content in the polymer, using less reactive crosslinkers (epoxies) or less reactive crosslinker accelerator systems and reducing the process temperature.
A cohesion improvement of the mass can be obtained by different routes. Either the accelerator concentration is increased, which reduces the processing time. It is also possible to increase the molecular weight of the polyacrylate while the accelerator concentration remains constant, which may be more efficient. In accordance with the invention, it is advantageous in any case to increase the crosslinker concentration (substances containing epoxide groups). Depending on the desired requirement profile of the mass or of the product, the abovementioned parameters must be suitably adapted.

Advantageous applications

The polyacrylates prepared according to the invention can be used for a wide range of applications. Below are some particularly advantageous applications exemplified.

The polyacrylate prepared by the process according to the invention is used in particular as a pressure-sensitive adhesive, preferably as a pressure-sensitive adhesive for an adhesive tape, the acrylate PSA being present as a single-sided or double-sided film on a carrier film.

These polyacrylates are particularly well suited if a high degree of application in one layer is required, since with this coating method an almost arbitrarily high mass application, preferably more than 100 g / m ² , more preferably more than 200 g / m ² , is possible, and although in particular at the same time particularly homogeneous crosslinking through the layer. Favorable applications, without being exhaustive, are for example technical adhesive tapes, in particular for use in construction, eg insulating tapes, anti-corrosion tapes, aluminum adhesive tapes, fabric-reinforced adhesive tapes, building tapes, eg vapor barriers, mounting tapes, cable tapes, self-adhesive films and / or paper labels ,

The polyacrylate prepared according to the invention can also be offered as a pressure-sensitive adhesive for a carrierless adhesive tape, as a so-called transfer adhesive tape. Again, the almost arbitrarily highly adjustable mass application at the same time particularly homogeneous crosslinking through the layer is particularly advantageous. Preferred basis weights are more than 10 g / m ² to 5000 g / m ² , particularly preferably 100 g / m ² to 3000 g / m ² .

The polyacrylate prepared according to the invention can also be present as a heat seal adhesive in transfer adhesive tapes or in single-sided or double-sided adhesive tapes. Again, for carrier-containing pressure-sensitive adhesive tapes, the carrier may be a viscoelastic polyacrylate obtained according to the invention.

An advantageous embodiment of the correspondingly obtained adhesive tapes can advantageously be used as a stripable adhesive tape, in particular in such a way that it can be removed again without residue by pulling essentially in the bonding plane.

The process of the invention is also particularly suitable for the production of three-dimensional pressure-sensitive or non-tacky shaped articles. A particular advantage of this method is that a layer thickness limitation of the polyacrylate to be crosslinked, to be formed, in contrast to UV and ESH curing process is not present. According to the choice of the coating or molding aggregates thus arbitrarily shaped structures can be produced, which can then post-cure under mild conditions to the desired strength.

This method is also particularly suitable for producing particularly thick layers, in particular pressure-sensitive adhesive layers or viscoelastic acrylate layers having a thickness of more than 80 μm. Such layers are difficult to produce with the solvent technique (blistering, very slow coating speed, laminating thin layers on top of each other is expensive and involves weak points).
For example, thick pressure-sensitive adhesive layers can be present unfilled as pure acrylate or resin-blended or filled with organic or inorganic fillers. Even after the known methods open-celled or closed-cell foamed layers are possible. As a foaming method, foaming by compressed gases such as nitrogen or CO _{2 is} possible, or foaming by blowing agents such as hydrazines or expandable microballoons. In the case of using expanding microballoons, the mass or the shaped layer is advantageously activated in a suitable manner by means of heat input. The foaming can take place in the extruder or after the coating. It may be expedient to smooth the foamed layer by means of suitable rollers or release films. To produce foam-like layers, it is also possible to add glass hollow spheres or already expanded polymeric microballoons to the pressure-sensitive adhesive thermally crosslinked acrylate hotmelt PSA.

In particular, this method can also be used to produce thick layers which can be used as a carrier layer for adhesive tape coated on both sides with a pressure-sensitive adhesive, in particular preferably filled and foamed layers which can be used as carrier layers for foam-like adhesive tapes. Even with these layers, it is useful to add full glass beads, hollow glass beads or expanding microballoons to the polyacrylate before adding the crosslinker-accelerator system or the crosslinker or the accelerator. In the case of using expanding microballoons, the mass or the formed layer is suitably activated by heat input. The foaming can take place in the extruder or after the coating. It may be expedient to smooth the foamed layer by means of suitable rollers or release films or by laminating a pressure-sensitive adhesive coated onto a release material. For such a foam-like, viscoelastic layer, a pressure-sensitive adhesive layer can be laminated on at least one side. Preferably, a corona-pretreated polyacrylate layer is laminated on both sides. Alternatively, differently pretreated adhesive layers, ie pressure-sensitive adhesive layers and / or heat-activatable layers based on others, can be used Polymers are laminated as acrylate-based to viskolelastischen layer. Suitable base polymers are natural rubber-based adhesives, synthetic rubbers, acrylate block copolymers, styrenic block copolymers, EVA, certain polyolefins, special polyurethanes, polyvinyl ethers, and silicones. However, preference is given to compositions which have no appreciable fraction of migratable constituents which are so well compatible with the polyacrylate that they diffuse in a significant amount into the acrylate layer and alter the properties there.

Instead of laminating a pressure-sensitive adhesive layer on both sides, a hot melt adhesive layer or thermally activatable adhesive layer can also be used on at least one side. Such asymmetric adhesive tapes allow the bonding of critical substrates with high bond strength. Such an adhesive tape can be used, for example, for fastening EPDM rubber profiles to vehicles.

A particular advantage of the thermally crosslinked polyacrylates is that these layers, whether used as a viscoelastic carrier, as a pressure-sensitive adhesive or as a heat-sealing compound, with the same surface quality no crosslinking profile through the layer (or correspondingly the molded articles produced from the polyacrylates) - in particular in contrast to UV and ESH crosslinked layers - show. As a result, the balance between adhesive and cohesive properties can be controlled and adjusted ideally for the entire shift by networking. In the case of radiation-crosslinked layers, on the other hand, one side or one sub-layer is always over- or under-crosslinked.

Experimental part

The following exemplary experiments are intended to illustrate the invention in more detail without the invention being unnecessarily restricted by the choice of the examples given.

Measurement methods (general): Solids content (measuring method A1);

The solids content is a measure of the proportion of non-volatile constituents in a polymer solution. It is determined gravimetrically by weighing the solution, then evaporating the vaporizable fractions for 2 hours at 120 ° C in a drying oven and weighing back the residue.

K value (according to FIKENTSCHER) (measuring method A2):

The K value is a measure of the average molecular size of high polymer substances. For measurement, one percent (1 g / 100 ml) of toluene polymer solutions were prepared and determined with the aid of a VOGEL OSSAG Viskositmeters their kinematic viscosities. After normalization to the viscosity of the toluene, the relative viscosity is obtained, from which, according to FIKENTSCHER, the K value can be calculated (Polymer 8/1967, 381 ff.).

Gel permeation chromatography GPC (measuring method A3):

The data on the weight-average molecular weight M _w and the polydispersity PD in this document relate to the determination by gel permeation chromatography. The determination takes place on 100 μl of clear filtered sample (sample concentration 4 g / l). The eluent used is tetrahydrofuran with 0.1% by volume of trifluoroacetic acid. The measurement takes place at 25 ° C. The precolumn used is a PSS-SDV column, 5 μ, 10 ³ Å, ID 8.0 mm × 50 mm. For separation, columns of the type PSS-SDV, 5 p, 10 ³ Å and 10 ⁵ Å and 10 ⁶ Å each having an ID of 8.0 mm × 300 mm are used (columns from Polymer Standards Service, detection by means of a differential refractometer Shodex RI71). , The flow rate is 1.0 ml per minute. The calibration is carried out against PMMA standards (polymethyl methacrylate calibration)].

Measuring methods (in particular pressure-sensitive adhesives): 180 ° bond strength test (measurement method H1):

A 20 mm wide strip of an acrylate PSA coated on polyester was applied to steel plates previously washed twice with acetone and once with isopropanol. The pressure-sensitive adhesive strip was pressed onto the substrate twice with a contact pressure corresponding to a weight of 2 kg. The adhesive tape was then immediately peeled off the substrate at a speed of 300 mm / min and at an angle of 180 °. All measurements were carried out at room temperature.
The measurement results are given in N / cm and are averaged out of three measurements. The adhesive force on polyethylene (PE) was determined analogously.

Shear life (measuring method H2):

A 13 mm wide and over 20 mm (for example 30 mm) strip of adhesive tape was applied to a smooth steel surface which was cleaned three times with acetone and once with isopropanol. The bonding area was 20 mm * 13 mm (length * width), with the adhesive tape projecting beyond the test panel at the edge (for example by 10 mm corresponding to the above-indicated length of 30 mm). Subsequently, the adhesive tape was pressed four times with a contact pressure corresponding to a weight of 2 kg on the steel beam. This sample was suspended vertically so that the protruding end of the adhesive tape faces down.
At room temperature, a weight of 1 kg was attached to the projecting end of the adhesive tape. The measurement is carried out under normal climatic conditions (23 ° C, 55% humidity) and at 70 ° C in a warming cabinet.
The measured shear times (times until complete detachment of the adhesive tape from the substrate, termination of the measurement at 10,000 minutes) are given in minutes and correspond to the average of three measurements.

Micro-shear test (measuring method H3)

This test serves to quickly test the shear strength of adhesive tapes under temperature load.

Sample preparation for micro-shear test:

An adhesive tape cut from the respective sample sample (length approx. 50 mm, width 10 mm) is glued onto a steel test plate cleaned with acetone, so that the Steel plate the tape protrudes to the right and left and that the tape over the test plate at the top by 2 mm. The bond area of the sample is height x width = 13mm x 10mm. The bonding site is then overrolled six times with a 2 kg steel roller at a speed of 10 m / min. The tape is reinforced flush with a sturdy tape that serves as a support for the distance sensor. The sample is suspended vertically by means of the test plate.

Micro Test:

The sample to be measured is loaded at the lower end with a weight of 100 g. The test temperature is 40 ° C, the test duration 30 minutes (15 minutes load and 15 minutes unloading). The shear distance after the specified test duration at constant temperature is given as the result in μm, as the maximum value ["max"; maximum shear distance through 15 minutes of exposure]; as minimum value ["min"; Shearing distance ("residual deflection") 15 min after discharge; Relief is followed by a return movement through relaxation]. Also indicated is the elastic fraction in percent ["elast"; elastic proportion = (max - min) * 100 / max].

Measuring methods (in particular three-layer constructions): 90 ° bond strength steel - open and covered side (measuring method V1):

The determination of the bond strength of steel is carried out at a test climate of 23 ° C +/- 1 ° C temperature and 50% +/- 5% rel. Humidity. The samples were cut to 20 mm width and glued to a steel plate. The steel plate is cleaned and conditioned before the measurement. For this purpose, the plate is first wiped with acetone and then left for 5 minutes in the air, so that the solvent can evaporate. The side of the three-layer composite facing away from the test substrate was then covered with a 50 μm aluminum foil, which prevents the pattern from stretching during the measurement. After that, the test pattern was rolled up on the steel substrate. For this purpose, the tape with a 2 kg roll 5 times back and forth, at a winding speed of 10 m / min, rolled over. Immediately after rolling up, the steel plate was pushed into a special holder, which makes it possible to pull the sample vertically at an angle of 90 ° C. The bond strength was measured with a Zwick tensile testing machine. When applying the covered side on the steel plate, the open side of the three-layer composite is initially against the 50 microns Laminated aluminum foil, the separating material removed and glued to the steel plate, rolled and measured analogously.
The results of both sides, open and covered, are given in N / cm and are averaged out of three measurements.

Shear life - open and covered side (measurement method V2):

The sample preparation was carried out in a test climate of 23 ° C +/- 1 ° C temperature and 50% +/- 5% rel. Humidity. The test piece was cut to 13 mm and glued to a steel plate. The bond area is 20 mm x 13 mm (length x width). Before the measurement, the steel plate was cleaned and conditioned. For this purpose, the plate is first wiped with acetone and then left for 5 minutes in the air, so that the solvent can evaporate. After bonding, the open side was reinforced with a 50 μm aluminum foil and rolled over twice with a 2 kg roller. Subsequently, a belt loop was attached to the protruding end of the three-layer composite. The whole was then hung on a suitable device and loaded with 10 N. The suspension device is designed so that the weight loads the sample at an angle of 179 ° +/- 1 °. This ensures that the three-layer composite can not peel off from the lower edge of the plate. The measured shear time, the time between hanging up and falling off of the sample, is given in minutes and is the mean of three measurements. To measure the covered side, the open side is first reinforced with the 50 μm aluminum foil, the separating material is removed and adhered to the test plate analogously to the description. The measurement is carried out under normal conditions (23 ° C, 55% humidity).

Wall hook test (measuring method V3)

FIG. 6 shows the preparation of the polyacrylate pressure-sensitive adhesive layers (layer A and / or C). A 30 mm x 30 mm test specimen (3.1) fixed between two polished steel plates (3.2) is pressed with 0.9 kN for 1 minute (force P). Then a 9 cm long lever arm (3.3) is screwed into the top steel plate and this then loaded with a 1000 g weight (3.4). Care is taken that the time between pressing and loading is not more than two minutes (t ≤ 2 min).
The holding time is measured, ie the time between hanging up and falling off the pattern. As a result, the holding time in minutes becomes the average of a triple determination specified. The test climate is 23 ° C +/- 1 ° C and 50% RH +/- 5% RH (RH RH).
In each case the open and the covered side were measured.

Commercially available chemicals used

Chemical compound trade name Manufacturer CAS-No. peroxydicarbonate bis (4-tert-butylcyclohexyl) Perkadox® 16 Akzo Nobel 15520-11-3 Terpene-phenolic adhesive resin (softening point 110 ° C, hydroxyl value 45-60) Dertophene® T110 DRT, France 73597-48-5 pentaerythritol tetraglycidyl Polypox® R16 UPPC AG 3126-63-4 triethylenetetramine Epikure® 3234 Epikure® 925 Hexion Specialty Chemicals 112-24-3 Isopropylated triaryl phosphate Reofos® 65 Great Lakes, United States 68937-41-7 diethylenetriamine Epikure® 3223 Hexion Specialty Chemicals 111-40-0 trimethylolpropane triglycidyl Polypox® R20 UPPC AG 30499-70-8 trimethyl Epikure® 940 Hexion Specialty Chemicals 25620-58-0 2,2'-azobis (2-methylpropionitrile), AIBN Vazo® 64 DuPont 78-67-1 Hollow glass spheres (density 0.28 g / cm ² , bulk density 0.16 g / cm ³ , particle diameter 5 - 115 μm [range], 65 μm [average value]) Q-Cel® Hollow Glass Spheres 5028 Potter's Industries Chalk (density 2.74 g / cm ³ , bulk density 0.56 g / cm ³ , pH 8.8-9.5, solubility [water] 16 mg / l, decomposition point 900 ° C) Mikrosöhl® 40 United Kreidewerke Dammann KG 1317-65-3 Thermoplastic hollow microspheres (particle size 10-17 μm, density max 0.017 g / cm ³ , expansion temperature 127-139 ° C [start], 164-184 ° C [max exp.]) Expancel® 092 DU 40 Akzo Nobel all specifications at 20 ° C;
Epikure® is also marketed under the trade names Epi-Cure® and Bakelite® EPH

Examples of pressure-sensitive adhesives Preparation of the Starting Polymers for Examples PSA B1 to B8

The preparation of the starting polymers is described below. The investigated polymers are conventionally prepared by free radical polymerization in solution.

Base polymer P1

A reactor conventional for radical polymerizations was charged with 45 kg of 2-ethylhexyl acrylate, 45 kg of n-butyl acrylate, 5 kg of methyl acrylate, 5 kg of acrylic acid and 66 kg of acetone / isopropanol (92.5: 7.5). After passage of nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C and 50 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h, 50 g of AIBN were again added and after 4 h was diluted with 20 kg of acetone / isopropanol mixture.
After 5 and after 7 h each was re-initiated with 150 g of bis (4-tert-butylcyclohexyl) peroxydicarbonate. After a reaction time of 22 hours, the polymerization was stopped and cooled to room temperature. The polyacrylate has a conversion of 99.6%, a K value of 59, a solids content of 54%, an average molecular weight of Mw = 557,000 g / mol, polydispersity PD (Mw / Mn) = 7.6.

Base polymer P2

A reactor conventional for radical polymerizations was charged with 47.5 kg of 2-ethylhexyl acrylate, 47.5 kg of n-butyl acrylate, 5 kg of acrylic acid, 150 g of dibenzoyl trithiocarbonate and 66 kg of acetone. After passage of nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C and 50 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h, 50 g of AIBN were again added. After 4 h, it was diluted with 10 kg of acetone. After 5 and after 7 h, 150 g each of bis (4-tert-butylcyclohexyl) peroxydicarbonate were added. After a reaction time of 22 hours, the polymerization was stopped and cooled to room temperature.
The polyacrylate has a conversion of 99.5%, a K value of 41.9, a solids content of 56.5%, an average molecular weight of Mw = 367,000 g / mol, polydispersity PD (Mw / Mn) = 2.8 ,

Base polymer P3

41.5 kg of 2-ethylhexyl acrylate, 41.5 kg of n-butyl acrylate, 15 kg of methyl acrylate, 1 kg of acrylic acid and 1 kg of 2-hydroxyethyl methacrylate (HEMA) in 66 kg of acetone / isopropanol (92.5: 7.5 ) polymerized. was initiated twice with 50 g of AIBN, twice with 150 g of bis (4-tert-butylcyclohexyl) peroxydicarbonate and diluted with 20 kg of acetone / isopropanol mixture (92.5: 7.5). After a reaction time of 22 hours, the polymerization was stopped and cooled to room temperature.
The polyacrylate has a conversion of 99.6%, a K value of 69.5, a solids content of 53.3%, an average molecular weight of Mw = 689,000 g / mol, polydispersity PD (Mw / Mn) = 7.8 ,

Base polymer P4

As in Example P1, 68 kg of 2-ethylhexyl acrylate, 25 kg of methyl acrylate and 7 kg of acrylic acid were polymerized in 66 kg of acetone / isopropanol (92.5: 7.5).
The polyacrylate has a conversion of 99.7%, a K value of 51, a solids content of 55.0%, an average molecular weight of Mw = 657,000 g / mol, polydispersity PD (Mw / Mn) = 8.2.

Process 1: Concentration / Preparation of the Hotmelt Adhesive Adhesive:

The acrylate copolymers (base polymers P1 to P4) are largely freed from the solvent by means of single-screw extruders (concentrating extruder, Berstorff GmbH, Germany) (residual solvent content ≦ 0.3% by weight, see the individual examples). By way of example, the parameters of the concentration of the base polymer P1 are shown here. The speed of the screw was 150 U / min, the motor current 15 A, it was realized a throughput of 58.0 kg liquid / h. For concentration, a vacuum was applied to 3 different domes. The negative pressures were each between 20 mbar and 300 mbar. The outlet temperature of the concentrated hot melt is approx. 115 ° C. The solids content after this concentration step was 99.8%.

Method 2: Preparation of Modified Hotmelt PSAs and Viscoelastic Supports

The acrylate hot-melt pressure sensitive adhesives prepared by process 1 described above were fed directly into a downstream WELDING twin-screw extruder (WELDING Engineers, Orlando, USA; Model 30 MM DWD; Screw diameter 30mm, length of screw 1 = 1258 mm; Length of screw 2 = 1081 mm; 3 zones). The resin Dertophene® T110 was metered into zone 1 via a solids metering system and mixed in homogeneously. In the case of the examples for the examples MT 1 and MP 2, no resin was added. In the examples MT 3, MT 4 and MT 5, the corresponding additives were metered in via the solids metering system and mixed in homogeneously. By way of example, the parameters for the resin compounding with the base polymer P1 are set forth here. Speed was 451 U / min, the motor current 42 A, it was a throughput of 30.1 kg / h realized. The temperatures of zones 1 and 2 were each 105 ° C, the melt temperature in zone 1 was 117 ° C and the melt temperature at exit (zone 3) at 100 ° C.

Method 3: Production of the Adhesive Tapes According to the Invention, Blending with the Vernetzer Accelerator System for Thermal Crosslinking and Coating.

The acrylate hot-melt pressure-sensitive adhesives prepared by processes 1 to 2 were melted in a feed extruder (single screw extruder from TROESTER GmbH & Co KG, Germany) and conveyed therewith as polymer melt into a twin-screw extruder (LEISTRITZ, Germany, designation LSM 30/34 The unit is electrically heated from the outside and air-cooled by means of various blowers and is designed so that a short residence time of the adhesive in the extruder is ensured with good distribution of the crosslinker-accelerator system in the polymer matrix The addition of the respective crosslinker and accelerator is carried out with suitable dosing equipment optionally at several points ( Fig.1 : Dosierstellen 1.1 and 1.2) and optionally using dosing aids in the pressure-free conveying zones of the twin-screw extruder.
After the finished compounded, ie mixed with the crosslinker accelerator system adhesive from the twin-screw extruder (outlet: round nozzle, 5 mm diameter), the coating is carried out after Fig.1 on a web-shaped carrier material. The time between addition of the crosslinker-accelerator system to molding or coating is referred to as processing time. The processing time indicates the period during which the adhesive mixed with the crosslinker-accelerator system or the viscoelastic carrier layer can be coated with an optically good line image (gel-free, speck-free). The coating takes place with web speeds between 1 m / min and 20 m / min, the doctor roller of the 2-Walzenauftragswerks is not driven.
In the following examples and in Tab.1 to Tab.3, the formulations used, the manufacturing parameters and the properties achieved are each described in more detail.

Example B1

• Pentaerthrittetraglycidether,
  hier Polypox® R16 der Fa. UPPC AG, Deutschland (Epoxid) und einem
• Triethylentriamin,
  hier Epikure® 3234 der Fa. HEXION, Deutschland (Aminbeschleuniger) compoundiert.

Detaillierte Beschreibung: In dem in Verfahren 3 beschriebenen Doppelschneckenextruder wurde ein Gesamtmassestrom bestehend aus 70 Teilen Polymer P1 und 30 Teilen Harz Dertophene® T110 von 533,3 g/min (das entspricht 373 Gramm des reinen Polymers pro Minute) mit 1,14 g/min des Epoxidvernetzers Pentaerythrittetraglycidether (entspricht 0,31 Gew.-% auf Polymer) und 1,89 g/min des Aminbeschleunigers Triethylentetramin (entspricht 0,51 Gew.% auf Polymer) abgemischt. Die Dosierung des Amins und des Epoxids erfolgt separat über zwei Schlauchpumpen an Dosierstelle 1.1 (sieh Fig.1). Zur Verbesserung der Dosierfähigkeit und der erreichbaren Mischgüte wurde das verwendete Vernetzersystem mit dem flüssigen Phophatester (Isopropyliertes Triarylphosphat; Reofos 65; Fa. GREAT LAKES, USA) verdünnt (Verhältnis zum Vernetzer 0,5:1). Die Prozessparameter sind in Tab. 2 zusammengefasst.
Die Verarbeitungszeit des fertigen Compounds war größer 7 min bei einer durchschnittlichen Massetemperatur von 125 °C nach dem Verlassen des LEISTRITZ-Doppelschneckenextruders. Die Beschichtung erfolgt an einem 2-Walzenauftragswerk gemäß Fig. 1 bei Walzenoberflächentemperaturen von jeweils 100 °C und einem Masseauftrag von 86 g/m² auf 23 µm PET-Folie. Von dem so hergestellten Klebeband wurden die Klebkraft auf Stahl bei Raumtemperatur und Mikroschwerwege bei 40 °C in Abhängigkeit der Lagerungsdauer gemessen. Nach 25 Tagen Raumtemperaturlagerung wird der maximale Mikroscherweg mit 160 µm bei einem elastischen Anteil von 75 % gemessen. Weitere klebtechnische Daten des Beispiels B1 sind in Tabelle 3 zusammengefasst. Mit diesem Beispiel wird gezeigt, dass sehr leistungsfähige Klebebänder hergestellt werden können, die sich unter anderem durch gute Klebkräfte auf polaren und unpolaren Substraten (Stahl und Polyethlyen) und gute kohäsive Eigenschaften auch unter Temperatureinfluss auszeichnen.The base polymer P1 is polymerized according to the polymerization process described, concentrated according to process 1 (solids content 99.8%) and then blended according to process 2 with Dertophene® T 110 resin. This resin-modified acrylate hot melt composition was then continuously prepared according to method 3 with the crosslinker-accelerator system consisting of a

• pentaerythritol tetraglycidyl,
  here Polypox® R16 the company. UPPC AG, Germany (epoxy) and a
• triethylenetetramine,
  here Epikure® 3234 from the company HEXION, Germany (amine accelerator) compounded.

Detailed Description: In the twin-screw extruder described in Method 3, a total mass flow consisting of 70 parts Polymer P1 and 30 parts Dertophene® T110 resin of 533.3 g / min (equivalent to 373 grams of pure polymer per minute) was 1.14 g / of the epoxide crosslinker pentaerythritol tetraglycidyl ether (corresponding to 0.31% by weight of polymer) and 1.89 g / min of the amine accelerator triethylenetetramine (corresponding to 0.51% by weight of polymer). The dosage of the amine and the epoxide is carried out separately via two peristaltic pumps at metering point 1.1 (see Fig.1 ). To improve the meterability and the achievable mixing quality, the crosslinker system used was diluted with the liquid phosphate ester (isopropylated triaryl phosphate, Reofos 65, GREAT LAKES, USA) (ratio to the crosslinker 0.5: 1). The process parameters are summarized in Tab.
The processing time of the finished compound was greater than 7 minutes at an average melt temperature of 125 ° C after leaving the LEISTRITZ twin-screw extruder. The coating is carried out on a 2-roll applicator according to Fig. 1 at roll surface temperatures of 100 ° C and a total application of 86 g / m ² on 23 microns PET film. Of the adhesive tape thus produced the bond strength to steel at room temperature and microgravity paths at 40 ° C were measured as a function of storage time. After 25 days of room temperature storage, the maximum micro-shear path is measured at 160 μm with an elastic fraction of 75%. Further adhesive technical data of Example B1 are summarized in Table 3. This example shows that very efficient adhesive tapes can be produced, which are characterized among other things by good adhesive forces on polar and non-polar substrates (steel and polyethylene) and good cohesive properties even under the influence of temperature.

Example B2

• Trimethylolpropantriglycidether,
  hier Polypox® R20, Fa. UPPC AG, Deutschland (Epoxid) und
• Diethylentriamine,
  hier Epikure® 3223, Fa. HEXION, Deutschland (Aminbeschleuniger).

Analog Beispiel B1 wurden 0,87 Gew.% des multifunktionellen Epoxides Trimethylolpropantriglycidether und 0,48 Gew.% des Amins Diethylentriamin (jeweils bezogen auf Acrylatcopolymer) gemäß Verfahren 3 zugesetzt. Die Extruderdrehzahl des LEISTRITZ-Doppelschneckenextruders betrug 125 Umdrehungen pro Minute, der Massedurchsatz 16,4 kg/h. Die Verarbeitungszeit betrug mehr als 5 min bei einer effektiven Massetemperatur von 108 °C nach dem Verlassen des Extruders. Mittels Walzenauftragswerk gemäß Fig. 1 wurden mit einem Masseauftrag von 101 g/m² auf 23 µm PET-Folie beschichtet.
Von dem so hergestellten Klebeband wurden Klebkraft-, Scherstandzeiten und Mikroschwerwegmessungen in Abhängigkeit von der Lagerungsdauer der Muster bei Raumtemperatur durchgeführt. Nach 25 Tagen Raumtemperaturlagerung wurden Scherteststandzeiten größer 10.000 min bei Raumtemperatur gemessen. Dieses Klebebandmuster wurde stark vernetzt, erkennbar an der sehr geringen maximalen Scherstrecke von nur 70 µm und einem hohen elastischen Anteil von 90 % gemäß Messmethode H3 "Mikroscherweg." Die Klebkraft auf Polyethlyen (PE) ist mit 2,5 N/cm erwartungsgemäß gering. Weitere klebtechnische Daten sind in Tabelle 3 unter Beispiel B2 aufgelistet.The base polymer P2 (residual solvent content: 0.1% by weight) concentrated according to process 1 and blended according to process 2 with resin Dertophene® T110 was compounded and coated analogously to example B1 according to process 3 in a twin-screw extruder with the crosslinker-accelerator system.
The crosslinker-accelerator system consists of

• trimethylolpropane triglycidyl ether,
  here Polypox® R20, UPPC AG, Germany (Epoxy) and
• diethylenetriamines,
  here Epikure® 3223, HEXION, Germany (amine accelerator).

0.87% by weight of the multifunctional epoxide trimethylolpropane triglycidyl ether and 0.48% by weight of the amine diethylenetriamine (in each case based on the acrylate copolymer) were added according to Example 3 in analogy to Example B1. The extruder speed of the LEISTRITZ twin-screw extruder was 125 revolutions per minute, the mass throughput 16.4 kg / h. The processing time was more than 5 minutes at an effective melt temperature of 108 ° C after leaving the extruder. By roller applicator according to Fig. 1 were coated with a mass application of 101 g / m ² on 23 micron PET film.
Adhesive, shearing and microgravity measurements were carried out on the thus prepared adhesive tape as a function of the storage period of the samples at room temperature. After 25 days of room temperature storage, shear test times greater than 10,000 minutes were measured at room temperature. This adhesive tape pattern was strongly cross-linked, recognizable by the very low maximum shear distance of only 70 μm and a high elastic content of 90% according to measurement method H3 "micro-shear path." The adhesive force on polyethylene (PE) is 2.5 N / cm expected low. Further adhesive data are listed in Table 3 under Example B2.

Example B3

• Pentaerthrittetraglycidether,
  hier Polypox® R16 der Fa. UPPC AG, Deutschland und
• Trimethylhexamethylendiamin,
  hier Epikure® 940 der Fa. HEXION, Deutschland.

Analog Beispiel B1 wurden 0,35 Gew.% des multifunktionellen Epoxides Pentaerythrittetraglycidether und 0,30 Gew.% des Amins Trimethylhexamethylendiamin (jeweils bezogen auf Acrylatcopolymer) zugesetzt. Dieses gegenüber den Beispielen B1 und B2 verwendete Polymersystem enthält weniger Acrylsäure, hat einen höheren K-Wert von 69,5 und ist bezüglich der kohäsiven Eigenschaften, den Scherstandzeiten bei 23 °C und 70 °C moderater eingestellt. Die Scherstandzeiten bei 23 °C liegen bei 1.600 min. Weitere Details zu massespezifischen Angaben befinden sich in Tabelle 1.The polymerization of the polymer P3 used, the concentration, the resin mixture and the incorporation of the crosslinker-accelerator system and the coating is carried out substantially as described in Example 1.
The networking system used here consists of

• pentaerythritol tetraglycidyl,
  here Polypox® R16 from UPPC AG, Germany and
• trimethylhexamethylenediamine,
  here Epikure® 940 of the company HEXION, Germany.

0.35% by weight of the multifunctional epoxide pentaerythritol tetraglycidyl ether and 0.30% by weight of the amine trimethylhexamethylenediamine (in each case based on acrylate copolymer) were added analogously to Example B1. This polymer system used with respect to Examples B1 and B2 contains less acrylic acid, has a higher K value of 69.5 and is more moderate in terms of cohesive properties, shearing life at 23 ° C and 70 ° C. Shear life at 23 ° C is 1.600 min. Further details on mass-specific information can be found in Table 1.

Example B4

The polymerization of the polymer P3 used, the concentration, the resin mixture and the incorporation of the crosslinker-accelerator system and the coating is carried out substantially as described in Example 1. By way of derogation, in addition, the filler chalk Mikrosöhl® 40 was incorporated in process 2, for which purpose the mixing screw geometries of the twin-screw extruder used were adapted accordingly. The crosslinker-accelerator system used here was chosen as in Example P3. 0.45% by weight of the multifunctional epoxide pentaerythritol tetraglycidyl ether and 0.40% by weight of the amine trimethylhexamethylenediamine (in each case based on acrylate copolymer) were added.
The average melt temperature after leaving the compounding extruder increased from 110 ° C. to 117 ° C. compared to the mass system from Example B3. Both the measured bond strengths of 9.4 and the shear rates of 3,800 minutes are improved over Example B3.
Further details on mass-specific information can be found in Table 1, for set process parameters in Table 2 and for adhesive-technical results in Table 3 in line B4.

Example B5

• Trimethylolpropantriglycidether,
  hier Polypox® R20, Fa. UPPC AG, Deutschland (Epoxid) und
• Diethylentriamine,
  hier Epikure® 3223, Fa. HEXION, Deutschland (Aminbeschleuniger).

Analog Beispiel B1 wurden 0,78 Gew.% des multifunktionellen Epoxides Trimethylolpropantriglycidether und 0,48 Gew.% des Amins Diethylentriamin (jeweils bezogen auf Acrylatcopolymer) gemäß Verfahren 3 zugesetzt. Die Extruderdrehzahl des LEISTRITZ-Doppelschneckenextruders betrug 100 Umdrehungen pro Minute, der Massedurchsatz 10 kg/h. Die Verarbeitungszeit betrug mehr als 5 min bei einer effektiven Massetemperatur von 114°C nach dem Verlassen des Extruders. Mittels Walzenauftragswerk gemäß Fig. 1 wurden mit einem Masseauftrag von 125 g/m² auf 23 µm PET-Folie beschichtet.The concentrated according to process 1 base polymer P4 (residual solvent content: 0.15 wt .-%) was compounded and coated analogously to Example B1 according to method 3 in a twin-screw extruder with the crosslinker-Beschleuiniger system.
The crosslinker accelerator system consists of

• trimethylolpropane triglycidyl ether,
  here Polypox® R20, UPPC AG, Germany (Epoxy) and
• diethylenetriamines,
  here Epikure® 3223, HEXION, Germany (amine accelerator).

As in Example B1, 0.78% by weight of the multifunctional epoxide trimethylolpropane triglycidyl ether and 0.48% by weight of the amine diethylenetriamine (in each case based on acrylate copolymer) were added according to Method 3. The extruder speed of the LEISTRITZ twin-screw extruder was 100 revolutions per minute, the mass throughput 10 kg / h. The processing time was more than 5 minutes at an effective melt temperature of 114 ° C after leaving the extruder. By roller applicator according to Fig. 1 were coated with a mass application of 125 g / m ² on 23 micron PET film.

Example B6 (comparative example)

• Das hier verwendete Vernetzungssystem besteht aus
  • Pentaerythrittetraglycidether,
    hier Polypox® R16 der Fa. UPPC AG, Deutschland und
  • Zinkchlorid.

Zugesetzt wurden 0,79 Gew.% des multifunktionellen Epoxides Pentaerythrittetraglycidether und 0,43 Gew.% Zinkchlorid.
Die gemessenen Scherwege gemäß Messmethode H3 "Mikroscherweg" werden nach 25 Tagen Lagerung bei Raumtemperatur zu größer als 2000 µm gemessen, der elastische Anteil beträgt 0 %, was bedeutet, dass keine oder keine nennenswerte Vernetzung stattgefunden hat.The polymerization of the polymer P1 used, the concentration, the resin mixture, the incorporation of the crosslinking component and the coating is carried out substantially as described in Example 1, but with the following variation:

• The networking system used here consists of
  • pentaerythritol tetraglycidyl,
    here Polypox® R16 from UPPC AG, Germany and
  • Zinc chloride.

0.79% by weight of the multifunctional epoxide pentaerythritol tetraglycidyl ether and 0.43% by weight of zinc chloride were added.
The measured shear paths according to measuring method H3 "micro-shear" are measured after 25 days of storage at room temperature to greater than 2000 microns, the elastic fraction is 0%, which means that no or no significant networking has taken place.

Repetition of measurements after temperature storage:

This adhesive tape pattern does not crosslink after storage for 6 days at 60 ° C, or after storage for one hour at 140 ° C in a warming cabinet. The adhesive tape samples were measured according to these storage conditions again with the measuring method H3 "micro-shear path" and the shear distances in turn determined to greater than 2000 microns.
Due to the lack of cross-linking, no further adhesive tests are carried out.
Further details on mass-specific information can be found in Table 1 and for the process parameters set in Table 2, each in line B6.

Example B7 (comparative example)

• Das hier verwendete Vernetzungssystem besteht nur aus
  • Triethylentetramin,
    hier Epikure® 3234 der Fa. HEXION, Deutschland.

In diesem Beispiel wird kein Epoxid eingesetzt.
Zugesetzt wurden 0,50 Gew.% des multifunktionellen Amins Triethylentetramin.
Die gemessenen Scherwege gemäß Messmethode H3 "Mikroscherweg" werden nach 25 Tagen Lagerung bei Raumtemperatur zu größer als 2000 µm gemessen, der elastische Anteil beträgt 0%, was bedeutet, dass keine oder keine nennenswerte Vernetzung stattgefunden hat.The polymerization of the polymer P1 used, the concentration, the resin mixture, the incorporation of the crosslinking component and the coating is carried out substantially as described in Example 1, but with the following variation:

• The networking system used here consists only of
  • triethylenetetramine,
    here Epikure® 3234 of the company HEXION, Germany.

In this example, no epoxy is used.
Added were 0.50% by weight of the multifunctional amine triethylenetetramine.
The measured shear paths according to measuring method H3 "micro-shear" are measured after 25 days of storage at room temperature to greater than 2000 microns, the elastic fraction is 0%, which means that no or no significant networking has taken place.

Repetition of measurements after temperature storage:

This tape pattern does not crosslink after 3 months of storage at 70 ° C, or after storage for one hour at 140 ° C in a warming cabinet. According to these bearings, the measurement method H3 "micro-shear path", which determines shear distances greater than 2000 μm, was again measured. Due to the lack of cross-linking, no further adhesive tests are carried out.
Further details on mass-specific information can be found in Table 1 and for the process parameters set in Table 2, each in line B7.

Example B8 (comparative example)

• Das hier verwendete Vernetzungssystem besteht nur aus
  • Pentaerthrittetraglycidether,
    hier Polypox® R16 der Fa. UPPC AG, Deutschland.

Zugesetzt wurden 0,31 Gew.% bezogen auf Polymer des multifunktionellen Epoxides Pentaerythrittetraglycidether.
In diesem Beispiel wird kein Amin eingesetzt.
Die gemessenen Scherwege gemäß Messmethode H3 "Mikroscherweg" werden nach 25 Tagen Lagerung bei Raumtemperatur zu größer als 2000 µm gemessen, der elastische Anteil beträgt 0 %, was bedeutet, dass keine oder keine nennenswerte Vernetzung stattgefunden hat.The polymerization of the polymer P1 used, the concentration, the resin mixture, the incorporation of the crosslinking component and the coating is carried out substantially as described in Example 1, but with the following variation:

• The networking system used here consists only of
  • pentaerythritol tetraglycidyl,
    here Polypox® R16 from UPPC AG, Germany.

0.31% by weight, based on the polymer of the multifunctional epoxide pentaerythritol tetraglycidyl ether, was added.
In this example no amine is used.
The measured shear paths according to measuring method H3 "micro-shear" are measured after 25 days of storage at room temperature to greater than 2000 microns, the elastic fraction is 0%, which means that no or no significant networking has taken place.

Repetition of measurements after temperature storage:

This tape pattern does not crosslink after being stored at 70 ° C for 3 months, or after storage for one hour at 140 ° C in a warming cabinet. Measured according to these storage conditions again with the measuring method H3 "micro-shear path", the shear distances were determined in each case greater than 2000 microns. Due to the lack of cross-linking, no further technical tests were carried out. Further details on mass-specific information can be found in Table 1 and for the process parameters set in Table 2, each in line B8.

When using the crosslinker-accelerator system according to the invention, the crosslinking reaction over the functional groups of the polyacrylate proceeds completely even without heat supply under normal conditions (room temperature). In general, after a storage time of 5 days to 14 days, the crosslinking reaction is completed so far that a functional adhesive tape or a functional carrier layer is present. The final cross-linking state and thus the final cohesion of the composition is, depending on the choice of the mass-crosslinker system after storage for 14 to 100 days, achieved in an advantageous form after 14 to 50 days storage at room temperature, expected earlier at higher storage temperature.

The crosslinking increases the cohesion of the adhesive and thus also the shear strength. These groups are known to be very stable. This allows very age-resistant and heat-resistant self-adhesive tapes.

On the other hand, it is apparent from consideration of Comparative Examples B6 to B8 that the crosslinking does not lead to success, if one does not use the crosslinker accelerator system according to the invention.

Examples Viscoelastic supports and three-layer structures I. Preparation of the PSA Polyacrylate adhesive 1 (PA1):

A conventional 100 L glass reactor for free-radical polymerizations was charged with 2.8 kg of acrylic acid, 8.0 kg of methyl acrylate, 29.2 kg of 2-ethylhexyl acrylate and 20.0 kg of acetone / isopropanol (95: 5). After passing nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C and 20 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h reaction time 20 g of AIBN was added again. After 4 and 8 h, the mixture was diluted with 10.0 kg each of acetone / isopropanol (95: 5) mixture. To reduce the residual initiators were added after 8 and after 10 h each 60 g of bis (4-tert-butylcyclohexyl) peroxydicarbonate. The reaction was stopped after 24 h reaction time and cooled to room temperature. Subsequently, the polyacrylate with 0.4 wt .-% aluminum (III) acetylacetonate (3% solution in isopropanol) was mixed, diluted to a solids content of 30% with isopropanol and then from solution onto a siliconized release film (50 microns of polyester ) coated. (Coating speed 2.5 m / min, drying channel 15 m, temperatures zone 1: 40 ° C, zone 2: 70 ° C, zone 3: 95 ° C, zone 4: 105 ° C), the application rate was 50 g / m ² ,

II. Preparation of viscoelastic supports manufacturing of the starting polymers For the viscoelastic Sluggish of the Examples VT 1 until 5

The preparation of the starting polymers is described below. The investigated polymers are conventionally prepared by free radical polymerization in solution.

Base polymer HPT 1

A reactor conventional for radical polymerizations was charged with 40 kg of 2-ethylhexyl acrylate, 40 kg of n-butyl acrylate, 15 kg of methyl acrylate, 5 kg of acrylic acid and 67 kg of acetone / isopropanol (95: 5). After passing nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C and 40 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h, 60 g of AIBN were added again, and after 4 h, the mixture was diluted with 14 kg of acetone / isopropanol mixture.
After 5 and after 7 h each was re-initiated with 150 g of bis (4-tert-butylcyclohexyl) peroxydicarbonate. After a reaction time of 22 hours, the polymerization was stopped and cooled to room temperature. The polyacrylate has a K value of 57, a solids content of 54.6%, an average molecular weight of Mw = 714,000 g / mol, polydispersity PD (Mw / Mn) = 7.6.

Base polymer HPT 2

As in Example 1, 65 kg of 2-ethylhexyl acrylate, 30 kg of tert-butyl acrylate and 5 kg of acrylic acid were polymerized in 67 kg of acetone / isopropanol (95: 5). was initiated twice with 50 g of AIBN, twice with 150 g of bis (4-tert-butylcyclohexyl) peroxydicarbonate and diluted with 20 kg of acetone / isopropanol mixture (95: 5). After a reaction time of 22 hours, the polymerization was stopped and cooled to room temperature.
The polyacrylate has a K value of 61.0, a solids content of 53.2%, an average molecular weight of Mw = 697,000 g / mol, polydispersity PD (Mw / Mn) = 7.1.

Base polymer HPT 3

The procedure was analogous to Example 1. For the polymerization, 60 kg of 2-ethylhexyl acrylate, 30 kg of styrene, 5 kg of methyl acrylate and 5 kg of acrylic acid were polymerized in 25 kg of ethyl acetate / isopropanol (97: 3). was initiated twice with 50 g each AIBN, twice with 150 g each of bis (4-tert-butylcyclohexyl) peroxydicarbonate (after 36 and 44 h reaction time) and diluted with 20 kg of ethyl acetate / isopropanol (97: 3). After a reaction time of 48 hours, the polymerization was stopped and cooled to room temperature. The polyacrylate has a K value of 61, a solids content of 68.4% and an average molecular weight of Mw = 567,000 g / mol, polydispersity PD (Mw / Mn) = 11.8.

Base polymer HPT 4

A reactor conventional for radical polymerizations was charged with 65 kg of 2-ethylhexyl acrylate, 30 kg of tert-butyl acrylate, 5 kg of acrylic acid, 100 g of benzyl dithiobenzoate and 67 kg of acetone. After passage of nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C and 50 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h, 50 g of AIBN were again added. After 4 h, it was diluted with 10 kg of acetone. After 5 and after 7 h, 150 g each of bis (4-tert-butylcyclohexyl) peroxydicarbonate were added. After a reaction time of 22 hours, the polymerization was stopped and cooled to room temperature.
The polyacrylate has a K value of 49.2, a solids content of 59.2%, an average molecular weight of Mw = 379,000 g / mol, polydispersity PD (Mw / Mn) = 3.1.

Base polymer HPT 5

A reactor conventional for radical polymerizations was charged with 68 kg of 2-ethylhexyl acrylate, 25 kg of methyl acrylate, 7 kg of acrylic acid and 66 kg of acetone / isopropanol (95: 5). After passing nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C and 40 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h, 60 g of AIBN were again added. After 4 h, it was diluted with 20 kg of acetone / isopropanol (95: 5). After 5 and after 7 h, 150 g each of bis (4-tert-butylcyclohexyl) peroxydicarbonate were added. After a reaction time of 22 hours, the polymerization was stopped and cooled to room temperature.
The polyacrylate has a K value of 55, a solids content of 55%, an average molecular weight of Mw = 579,000 g / mol, polydispersity PD (Mw / Mn) = 7.9.

Concentration and compounding of the base polymers HPT 1-5 for the viscoelastic carriers:

The acrylate copolymers HPT 1-5 are freed from the solvents analogously to process 1 and, if appropriate, then admixed with additives in analogy to process 2, cf. the individual examples.

Method 4: Production of the 3-layer structures by means of 2-roll calenders

The procedure was as in Fig. 5 described carried out. By means of the distributor nozzle (1), the viscoelastic material (3) which has been completely compounded with the crosslinker-accelerator system and optionally fillers is fed to the nip. The shaping of the viscoelastic mass into a viscoelastic film takes place between the calender rolls (W1) and (W2) in the nip between two self-adhesives (6a, 6b), which in turn are coated on anti-adhesively treated carrier materials (5a, 5b). At the same time, the viscoelastic composition is shaped to the set layer thickness and coated with the two supplied self-adhesives. In order to improve the anchoring of the self-adhesive compositions (6a, 6b) on the molded, viscoelastic carrier layer (4), the self-adhesive compositions are coronated by means of a corona station (8) before being fed into the nip (corona apparatus from VITAPHONE, Denmark, 100th W • min / m ² ). This treatment leads after the production of the three-layer composite to an improved chemical bonding to the viscoelastic support layer.
The web speed when passing through the coating system is 30 m / min. After leaving the nip, if necessary, an anti-adhesive carrier (5a) is uncovered and the finished three-layer product (9) is wound up with the remaining second anti-adhesive carrier (5b).
Specific examples of the preparation of the self-adhesive compositions and coating of the adhesive tapes according to the invention are presented below, without the invention being unnecessarily restricted by the choice of the stated formulations, configurations and process parameters.

Example MT 1

The base polymer HPT1 was concentrated according to process 1 (solids content 99.7%) and then continuously in accordance with process 3 in the twin-screw extruder with the crosslinker-accelerator system consisting of trimethylolpropane triglycidyl ether (Polypox® R20, 0.48% by weight, based on the polyacrylate) and diethylenetriamine (Epikure® 3223, 0.40% by weight, based on the polyacrylate).
The coating for producing the viscoelastic carrier VT1 from the base polymer HPT1 between the previously coated on siliconized polyester films mass layers PA 1 takes place on 2-Walzenauftragswerk at roller temperatures of 100 ° C according to method 4. The layer thickness of the viscoelastic carrier VT 1 was 800 microns. The Coronaleistung was 100 W · min / m ² . After 7 days of room temperature storage, the adhesive data were measured from the open and covered sides, respectively. The data of Example MT 1 are summarized in Table 4.

Example MT 2

The base polymer HPT2 was concentrated in accordance with process 1 (solids content 99.8%) and then continuously in accordance with process 3 in the twin-screw extruder with the crosslinker-accelerator system consisting of trimethylolpropane triglycidyl ether (Polypox® R20, 0.56% by weight, based on the polyacrylate). and diethylenetriamine (Epikure® 3223; 0.40% by weight based on the polyacrylate). Subsequently, as in Example 1, in each case previously coated on siliconized polyester films mass layers PA 1 at the 2-Walzenauftragswerk according to method 3 coated. The layer thickness of the viscoelastic carrier VT 2 was 850 μm. The Coronaleistung was 100 W · min / m ² . After 7 days of room temperature storage, the adhesive data of the open and covered sides were measured. The data of Example MT 2 are summarized in Table 4.

Example MT 3

The base polymer HPT3 was concentrated by process 1 (solids content 99.7%) and then compounded according to process 2 with 6.5% by weight hollow glass spheres Q-CEL® 5028 (from Potters Industries) and continuously mixed with the process according to process 3 in a twin-screw extruder Crosslinking accelerator system consisting of trimethylolpropane triglycidyl ether (Polypox® R20, 0.56 wt .-% based on the polyacrylate) and diethylenetriamine (Epikure® 3223, 0.80 wt .-% based on the polyacrylate) compounded. The coating for producing the viscoelastic carrier VT3 between the previously coated on siliconized polyester films mass layers PA 1 is carried out at 2-Walzenauftragswerk at roll temperatures of 100 ° C according to method 3. The layer thickness of the viscoelastic carrier VT 3 was 800 μm. The Coronaleistung was 100 W · min / m ² . After 7 days of room temperature storage, the adhesive data of the open and covered sides were measured. The data of Example MT 3 are summarized in Table 4.

Example MT 4

The base polymer HPT 4 was concentrated in accordance with process 1 (solids content 99.7%), then blended according to process 2 with 18 wt .-% micro-ocher chalk (Mikrosöhl® 40) and according to process 3 in a twin-screw extruder continuously with the crosslinker-accelerator system consisting of trimethylolpropane triglycidyl ether (Polypox® R20, 0.34% by weight, based on the polyacrylate) and diethylenetriamine (Epikure® 3223, 0.42% by weight, based on the polyacrylate). The coating for producing the viscoelastic carrier VT4 between the previously coated on siliconized polyester films mass layers PA 1 is carried out at 2-Walzenauftragswerk at roller temperatures of 100 ° C according to method 3. The layer thickness of the viscoelastic carrier VT 4 was 800 microns. The corona power was 100 W • min / m ² . After 7 days of room temperature storage, the adhesive data of the open and covered sides were measured. The data of Example MT 4 are summarized in Table 4.

Example MT 5

The base polymer HPT 5 was concentrated according to process 1 (solids content 99.8%), then mixed according to process 2 with 3 wt .-% unexpanded hollow microspheres Expancel® 092 DU 40 (Akzo Nobel, Germany) and according to process 3 in a twin-screw extruder continuously compounded with the crosslinker-accelerator system consisting of trimethylolpropane triglycidyl ether (Polypox® R20; 0.54% by weight based on the polyacrylate) and diethylenetriamine (Epikure® 3223; 0.42% by weight based on the polyacrylate). By introducing heat, the mixture was expanded in the extruder and then coated between the previously coated on siliconized polyester films mass layers PA 1 according to method 3 at roll temperatures of 130 ° C. The layer thickness of the expanded viscoelastic carrier VT 5 was 800 μm. The Coronaleistung for pretreatment of the pressure-sensitive adhesive layers was 100 W · min / m ² . After 7 days of room temperature storage, the adhesive data of the open and covered sides were measured. The data of Example MT 5 are summarized in Table 4.

As can be seen from the data in Table 4, the inventive double-sided adhesive assembly tapes have very good technical adhesive data. Particularly positive is the balanced adhesive profile of the respective pages. With the same layer of adhesive on both sides of the adhesive tape, these show almost the same adhesive technical data. This shows the homogeneous cross-linking through the layer. This is surprising for the skilled person. In addition, these three-layer adhesive tapes show no delamination. The anchoring of the layers to one another is very good due to the corona treatment of the pressure-sensitive adhesive layers and the postcrosslinking of the adjacent viscoelastic support layer. Table 1: Mass-specific information Compounding according to method 2 example Base polymer K value Polymer and aggregates Starting materials and quantities crosslinkers % By weight on polymer [] accelerator B1 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 Polypox® R16 0.31 Epikure® 3234 0.51 B2 P2 41.9 70 parts of polymer P2 + 30 parts of resin DT 110 Polypox® R20 0.87 Epikure® 3223 0.48 B3 P3 69.5 70 parts of polymer P3 + 30 parts of resin DT 110 Polypox® R16 0.35 Epikure® 940 0.30 B4 P3 69.5 49 parts polymer P3 + 21 parts resin DT 110 + 30 parts chalk Mikrosöhl® 40 Polypox® R16 0.45 Epikure® 940 0.40 B5 P4 51 100 parts of polymer P4 Polypox® R20 0.78 Epikure® 3223 0.48 B6 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 Polypox® R16 0.79 zinc chloride 0.43 B7 P1 59 70 parts polymer P1 + 30 parts resin DT110 / / Epikure® 3234 0.50 B8 P1 59 70 parts polymer P1 + 30 parts resin DT110 Polypox® R16 0.31 / / K value = measuring method A2
DT 110 = Dertophene® T110 example base polymer Compounding according to method 2 process parameters polymer K value Proportion of aggregates Throughput total mass DSE [kg / h] Speed DSE [1 / min] Nominal current consumption DSE [A] Pressure output DSE [bar] Massetemp. according to DSE [° C] RakelwalzeRW Coating roller BW Processing time [min] [] [] [] B1 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 32.0 110 15 12 125 100 100 bigger 7 B2 P2 41.9 70 parts of polymer P2 + 30 parts of resin DT 110 16.4 125 7 5 108 100 100 greater than 5 B3 P3 69.5 70 parts of polymer P3 + 30 parts of resin DT 110 12.0 110 8th 10 110 100 100 greater than 5 B4 P3 69.5 49 parts polymer P3 + 21 parts resin DT 110 + 30 parts chalk Mikrosöhl® 40 16.0 120 10 15 117 100 100 bigger 7 B5 P4 51 Polymer P4 10.0 100 14 20 114 100 100 greater than 5 B6 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 15.0 100 9 11 111 100 100 greater than 10 B7 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 16.0 100 11 10 118 100 100 greater than 10 B8 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 15.0 100 9 8th 115 100 100 greater than 10 DSE = twin-screw extruder; DT 110 = Dertophene® T110 example base polymer Compounding process 2 Adhesive properties after storage of the samples for 25 days at room temperature polymer K value Proportion of aggregates support film application rate Bond strength steel Adhesive power PE Shear life 10N, 23 ° C Shear life 10N, 70 ° C MSW 40 ° C elast. proportion of [] [] [] [] [g / m ² ] [N / cm] [N / cm] [Min] [Min] [Microns] / [%] B1 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 23μm PET film 86 98 4.6 > 10,000 80 160/75 B2 P2 41.9 70 parts of polymer P2 + 30 parts of resin DT 110 23μm PET film 101 8.5 2.5 > 10,000 30 70/90 B3 P3 69.5 70 parts of polymer P3 + 30 parts of resin DT 110 23μm PET film 79 8.1 3.4 1600 15 512/67 B4 P3 69.5 49 parts polymer P3 + 21 parts resin DT 110 + 30 parts chalk Mikrosöhl® 40 23μm PET film 98 9.4 2.9 3800 28 430/73 B5 P4 51 only polymer P4 23μm PET film 125 8.6 2.5 10,000 5670 960/79 B6 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 23μm PET film 105 Tests not possible, formulation is not networked. greater than 2000/0 B7 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 23μm PET film 75 Tests not possible, formulation is not networked greater than 2000/0 B8 P1 59 70 parts of polymer P1 + 30 parts of resin DT 110 23μm PET film 81 Tests not possible, formulation is not cured greater than 2000/0 Bond strength steel / PE = measuring method H1
Shear life = measurement method H2
MSW = micro-shear = measurement H3
DT 110 = Dertophene® T110 example Multilayered product Carrier thickness [μm] Adhesive strength steel, [N / cm] Shear life 10 N 23 ° C [min] Wall hook test [min] MSW 40 ° C / elastic. Share [μm] / [%] Pressure-sensitive adhesive 1 Viscoelastic carrier layer Pressure sensitive adhesive 2 open side covered page open side covered page open side covered page MT 1 50 g / m ² PA 1 VT 1 50 g / m ² PA 1 800 14.2 13.7 > 10000 > 10000 2580 2795 950/76 MT 2 50 g / m ² PA 1 VT 2 50 g / m ² PA 1 850 11.8 11.6 7850 6970 4876 4456 877/78 MT 3 50 g / m ² PA 1 VT 3 50 g / m ² PA 1 800 13.7 14.2 > 10000 > 10000 9320 9360 546/69 MT 4 50 g / m ² PA 1 VT 4 50 g / m ² PA 1 800 10.7 10.6 > 10000 > 10000 7540 7468 738/75 MT5 50 g / m ² PA 1 VT 5 50 g / m ² PA 1 800 13.5 13.6 > 10000 > 10000 > 10000 > 10000 1067/78 Bond strength steel = measurement method V1
Shear life = measurement method V2
Wall hook test = measuring method V3

Claims (18)

Crosslinker-accelerator system for the thermal crosslinking of polyacrylates having functional groups which are suitable for entering into linking reactions with epoxide groups, comprising at least one substance containing epoxide groups (crosslinkers) and at least one substance accelerating at a temperature below the melting temperature of the polyacrylate for the linking reaction ( Accelerator). Crosslinker-accelerator system according to claim 1, characterized in that are used as accelerators amines. Crosslinker-accelerator system according to claim 2, characterized in that tertiary amines are used as accelerators. Crosslinker-accelerator system according to one of claims 2 or 3, characterized in that are used as accelerators mulitifuktionelle amines. Crosslinker-accelerator system according to claim 1, characterized in that are used as accelerators phosphines or phosphonium compounds. Crosslinker-accelerator system according to one of the preceding claims, characterized in that
as epoxide group-containing substance multifunctional epoxides are used. Crosslinker-accelerator system according to one of the preceding claims, characterized in that
bifunctional epoxides, ie those containing two Epoxidgrupopen be used as the epoxide group-containing substance. Process for the thermal crosslinking of polyacrylates with functional groups which are suitable for entering into linking reactions with epoxide groups, characterized by
the use of a crosslinker-accelerator system comprising epoxide group-containing substances (crosslinkers) and at least one in a Temperature below the melting temperature of the polyacrylate for the linking reaction accelerating substance (accelerator). A method according to claim 8, characterized by
A crosslinker-accelerator system according to any one of claims 2 to 7. A method according to claim 8 or 9, characterized in that
the functional groups of the polyacrylates are selected from the group comprising carboxyl groups, hydroxy groups, acid anhydride groups, sulfonic acid groups, phosphonic acid groups. Method according to one of claims 8 to 10, characterized in that
initiating crosslinking in the melt of the polyacrylate in the presence of the crosslinker-accelerator system and thereafter cooling it at a time when the crosslinking reaction is less than 10% complete, provided that the crosslinking reaction proceeds even after cooling; until the finite degree of crosslinking is reached. A method according to claim 11, characterized in that
the cooling takes place to substantially room temperature. Method according to one of the preceding claims, characterized in that the initiation takes place in a processing reactor, the polyacrylate is removed after initiation from the processing reactor and coated on a permanent or temporary carrier and the polyacrylate in the coating or immediately after the coating in Main room temperature is cooled. Use of a polyacrylate prepared as claimed in any one of claims 8 to 13 as a pressure-sensitive adhesive. Use according to claim 14 for a pressure-sensitive adhesive tape coated on one or both sides with the pressure-sensitive adhesive. Use according to claim 14 for a carrierless adhesive tape. Use of a polyacrylate prepared according to any one of claims 8 to 13 as a heat sealant. Use of a polyacrylate prepared according to any one of claims 8 to 13 as a carrier material, in particular for an adhesive tape coated on one or both sides with a pressure-sensitive adhesive.

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